741 lines
34 KiB
Plaintext
741 lines
34 KiB
Plaintext
Message-ID: <073310Z08071994@anon.penet.fi>
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Newsgroups: alt.drugs
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From: an58264@anon.penet.fi (Dalamar)
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Date: Fri, 8 Jul 1994 07:25:09 UTC
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Subject: CHEMISTRY: Bonding and Structure
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In the following file the numbers immediately following an atoms symbol in
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a chemical formula should be read as subscript eg C2H6 should be read :
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CCCCCC H H
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C H H
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C H H
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C HHHHHHH 6
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C 222 H H 6
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C 2 H H 6 6
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CCCCCC 22 H H 6 6
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2222 66
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The mole is a measure of amount of substance in chemistry and is equivalent to
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6.02 x 10(raised to the power of 23) particles.
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Bonding and Structure
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_____________________
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The vast majority of substances which occur freely in nature, or are
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synthetically manufactured by man, are not comprised of free atoms,
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but of atoms held joined together by chemical bonds. How and why do atoms
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form bonds ?
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Obviously the formation of a bond must be energetically favourable, leading to a
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minimum of energy ie the product in which the bonds have been formed must be
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more stable than the individual atoms, otherwise the bonds would not form.
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To understand what happens in terms of electronic structure when atoms form
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bonds consider the group 0 elements. These comprise the inert gases helium,
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neon, argon, krypton, xenon and radon, all of which are noted for their extreme
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lack of chemical properties and unreactivity. Atoms of the noble gases do not
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normally react with any other atoms, so that the gases consist of atoms alone.
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This lack of reactivity and the fact that the gases are comprised of lone atoms
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indicates that these atoms are extremely stable, their energy being at such a
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favourable minimum that it cannot be improved by bond formation. The inert gases
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all have one thing in common - a complete outer shell of electrons, so we
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conclude that this is a very stable arrangement.
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The electrons contained in the outermost shell of an atom are generally the ones
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concerned with bonding and the formation of _compounds_. When two or more
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different elements are combined together, so that their atoms become bonded,
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the resultant substance is called a compound. The properties of the compound
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usually differs radically from the elements which combined together to
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form it. A classic example is the formation of water from the elements
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hydrogen and oxygen. When hydrogen and oxygen are mixed in the correct
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proportions and a spark or flame applied, a violent reaction occurs in which
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the hydrogen and oxygen react together to form water. Both oxygen and hydrogen
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are gases at room temperature, but the product of their reaction together is
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a clear liquid, without which life would not exist.
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When atoms form bonds they do so in such a way as to attain a stable electronic
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configuration. As we have already shown, the most stable configuration is that
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of a complete outer shell of electrons. There are three ways in which atoms may
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obtain a stable electronic configuration : by losing, gaining or sharing
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electrons. If we divide the elements into (a) electropositive elements, whose
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atoms compete poorly for electrons and give up one or more electrons fairly
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readily (low ionisation energy), (b) electronegative elements, whose atoms
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attract electrons strongly and also readily take up electrons, then the
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following rule of thumb applies :
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Electropositive element + Electronegative element = Ionic Bond
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Electronegative element + Electronegative element = Covalent Bond
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Electropositive element + Electropositive element = Metallic Bond
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The three modes of bonding described above are :
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1. The Ionic Bond.
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The _ionic bond_ is formed when electrons are transferred from one atom to
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another, generating cations and anions which are held together by the pure
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electrostatic attraction of the resulting positive and negative charges.
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Compounds such as sodium chloride (NaCl), iron sulphide (FeS) and magnesium
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oxide (MgO) contain this type of bonding.
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2. The Covalent bond.
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The _covalent bond_ is formed by the mutual sharing of electrons between
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two atoms. Each atom achieves a stable configuration by gaining a share of
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a number of electrons from the outermost shell of the other atom. Compounds
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such as methane (CH4), chloroform (CHCl3), hydrogen chloride (HCl) and
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benzene (C6H6) contain this type of bonding.
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3. The metallic bond.
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This type of bonding, as the name suggests, occurs in metals. The outermost
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electrons of the metal become _delocalised_, that is they are not associated
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with any one particular atom, but are free to move from atom to atom in the
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metal crystal. The structure can then be imagined as an array of metal cations
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surrounded by a delocalised 'sea' of electrons which hold the cations together.
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The outstanding electrical conductivity of metals is due to the mobility of
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these electrons through the lattice. Sodium metal consists of an array of
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Na+ cations (noble gas config. of neon, K2 L8) held together by the delocalised
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M1 electrons (sodium originally K2 L8 M1).
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Ionic and covalent bonding is covered in more detail below.
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The Ionic Bond
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______________
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Consider sodium, an electropositive element with low ionisation energy and
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electronic configuration of K2 L8 M1. When sodium reacts with an electronegative
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element, for example chlorine, the single electron contained in the M shell is
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readily lost to give Na+ ion, with the stable electronic configuration of neon,
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K2 L8. Chlorine, which is of high electronegativity (electron attracting),
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accepts an electron readily to give the _chloride ion_, Cl-, with the stable
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electronic configuration of argon, K2 L8 M8. By the transfer of only one
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electron, from sodium to chlorine, each atom is now 'happier' as it has achieved
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a more stable electron configuration. The millions of Na+ and Cl- ions which are
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generated during the reaction form themselves into a regular three dimensional
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cubic lattice, consisting of alternating Na+ and Cl- ions. Each Na+ ion in
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the lattice is surrounded by 6 Cl- ions, 4 in the same plane, one in the plane
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above, and one in the plane below. The diagram below shows a small portion of
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a single plane of Na+ and Cl- ions as they are arranged in sodium chloride.
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Na+ Cl- Na+ Cl- Na+ Cl- Na+
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Cl- Na+ Cl- Na+ Cl- Na+ Cl-
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Na+ Cl- Na+ Cl- Na+ Cl- Na+
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Cl- Na+ Cl- Na+ Cl- Na+ Cl-
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Na+ Cl- Na+ Cl- Na+ Cl- Na+
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This pattern will repeated not only in the same plane, but also in planes
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stacked above and below. The planes immediately above and below this one will
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be arranged so that the chloride ions they contain are above and below the
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sodium ions in this plane. The _coordination number_ of each ion is _six_.
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The electrostatic attractive forces between the ions are extremely strong,
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resulting in a rigid crystal structure and a compound which is a solid.
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The chemical formula for sodium chloride is written as NaCl, which represents
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the ratio of sodium ions to chloride ions in the compound.
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Because the rest of the group I metals (Li, Na, K etc) have similair electronic
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structure (one electron in outermost shell), they also have similair properties
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(electropositive, low ionisation energy) and can be expected to react in a
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similair fasion to sodium with chlorine, or any of the other of the group VII
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elements (commonly known as the halogens, F, Cl, Br etc), which are all one
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electron short of an inert gas structure. The resultant compounds will be of
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the general formula MX, where M represents an alkali metal and X a halogen.
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Some examples are sodium fluoride (NaF), lithium chloride (LiCl) and potassium
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iodide (KI).
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The group II elements are also electropositive and are collectively known as the
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alkaline earth metals. All of the metals in this group contain 2 electrons in
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the outermost shell of their atoms, for example the electronic structure of
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magnesium is K2 L8 M2. In combining with a halogen, an ionic compound of general
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formula MX2 is formed, where M represents an alkaline earth metal and X a
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halogen. To obtain an inert gas structure each metal atom must lose 2 electrons.
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However, each halogen atom requires but one electron to complete its outermost
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shell, therefore for each M(2+) cation formed there are two X(-) ions also
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formed, giving a chemical formula of MX2. Examples are magnesium chloride
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(MgCl2) and calcium fluoride (CaF2).
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Oxygen is another very electronegative element and with the electronic structure
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K2 L6, an oxygen atom is two electrons short of attaining the inert gas
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structure of neon (K2 L8). In compounds with the group I or group II metals,
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oxygen can accept two electrons to form the _oxide ion_, O(2-), which now has
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the inert gas structure of neon. Each group I metal atom donates only one
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electron, therefore the resulting _group I oxides_, have the general formula
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M2O eg. sodium oxide (Na2O). Each group II metal donates two electrons, giving
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a general formula of MO for the _group II oxides_, eg. magnesium oxide (MgO).
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The bonding in these oxides is again ionic (e.pos element + e.neg element).
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Most of the oxides, although stable, must be prepared by indirect methods as
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combustion in air gives other products such as peroxides and superoxides.
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The amount of energy released when one mole of an ionic compound is formed
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from its constituent ions is known as the _lattice energy_. This figure is
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usually quite high (eg approx 750 kJ/mol for NaCl) and depends on the nature
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of the ions and which type of structure they adopt. As well as the NaCl type
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of lattice which most of the group I halides adopt, many other geometries are
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formed by other ionic compounds. The reason why any particular geometry is
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adopted is that the lattice energy is at its most favourable.
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The Covalent Bond
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_________________
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When two electronegative elements react together, ionic bonds are not formed
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because both atoms have a tendency to gain electrons. However, both atoms may
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still achieve an inert gas structure by the mutual sharing of electrons.
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Consider the element chlorine, which has seven electrons in the outermost shell
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of its atoms. Chlorine exists under normal conditions as a yellow gas composed
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of discrete Cl2 molecules. Now consider how two chlorine atoms will combine to
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form a chlorine molecule (Cl2). If each atom gives a _share_ of one of its
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outermost electrons to the other, each achieves a full outer shell. As both
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chlorine atoms are of identical electronegativity, the pair of electrons
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which now constitute a covalent bond are shared equally between both atoms.
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Diagramatically this may be represented:
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x x x x x x x x
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x x x x x x x
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Cl + Cl =====> Cl Cl
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x x x x x
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x x x x x x x x
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Chlorine atoms A chlorine molecule
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Only the outermost electrons are shown in the diagram (the M shell).
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Each chlorine atom in the chlorine molecule has in its outermost shell six
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electrons which fully belong to it, plus a share in two more electrons, making
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a stable octet (inert gas structure of argon, K2 L8 M8) around each atom.
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A single covalent bond is therefore made up of a shared _pair_ of electrons.
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A carbon atom is four electrons short of a complete outer shell, therefore
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it will need to share four electrons and form four bonds. For example, a
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molecule of carbon tetrachloride is composed of one carbon atom bonded to
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four chlorine atoms, CCl4. Each chlorine atom is only one electron short of
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a complete outer shell, so each Cl atom forms only one bond.
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Diagramatically this may be represented:
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x x
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x x
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Cl
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x x
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x x x x x x x x x
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x x x x x x
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x C x + 4 Cl ======> Cl C Cl
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x x x x x
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x x x x x x x x x
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x x
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Cl
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x x
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x x
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Only the outer shell of electrons is shown for each atom.
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By sharing electrons in this way, both the carbon and all four chlorine atoms
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attain an inert gas structure. Although these equations and diagrams help us
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to rationalise the bonding in CCl4, it does not neccessarily follow that the
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atoms will react directly together. In the case of CCl4, carbon and chlorine
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do not react directly to CCl4 and carbon tetrachloride must be prepared by
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indirect reactions.
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Nitrogen is three electrons short of attaining an inert gas structure and will
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therefore form three covalent bonds to other atoms. Ammonia has the chemical
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formula NH3 and is produced by the direct reaction of hydrogen and nitrogen
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at high pressures :
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3 H2 + N2 = 2 NH3
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Hydrogen atoms are one electron short of attaining the inert gas structure of
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helium (K2). Each H atom is therefore capable of forming one covalent bond, as
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in ammonia (NH3).
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H
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x x
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x x
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N H
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x x
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x x
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H
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For the N atom, only the outer electrons are shown.
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Notice in the structure for ammonia that there are two electrons on the nitrogen
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which do not form bonds. These two electrons are known as a _lone pair_ and play
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an important role in the properties of ammonia and its derivatives.
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The bond which a pair of electrons form is more usually represented by a
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straight line joining the two atoms, and a lone pair by two dots next to the
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atom to which they belong. Thus ammonia can be more neatly represented by
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H
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:N-H The structural formula of the ammonia molecule with its
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| 3 single covalent bonds between N and H, plus a single
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H lone pair situated on nitrogen.
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Each bond line therefore represents a pair of electrons, which can be considered
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to be in the outer shell of both the atoms it joins. Each H atom has its
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required 2 electrons in the K shell, the nitrogen has 3 bond pairs, plus
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its lone pair, making a total of 3x2+2 = 8 electrons in its outermost shell
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which is the inert gas structure of neon (K2 L8). This is the _structural
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formula_ of ammonia and shows us the order in which the atoms are connected.
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The _molecular formula_ for a compound shows us which atoms are present and
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their numbers, but there could be many ways of fitting the atoms together so
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that each still forms its required number of bonds. Therefore, it is important
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to have a way of systematically naming all compounds in such a way that the
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structural formula can be worked out simply from the name. Even though such
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a system of naming has been in force a long time, some old common names are
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still in use. Some large molecules, which commonly have very long systematic
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names are generally referred to by an agreed common name. Compounds which
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share the same molecular formula, but differ in the way their atoms are
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connected or spatially arranged, are known as _isomers_. For example
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ethanol and dimethylether are related as _structural isomers_ because
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although they share the same molecular formula C2H6O, the way in which the
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atoms are connected differs :
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H H H H
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H-C-O-C-H H-C-C-O-H Ethanol and Dimethylether
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| | | | structural formulas.
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H H H H
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Dimethylether Ethanol
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C2H6O C2H6O
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Two other types of isomerism that are important are known as geometrical and
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optical.
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As well as single covalent bonds, double and triple covalent bonds also
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exist. For a double bond, two pairs of electrons are mutually shared between
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the atoms and for a triple bond three pairs of electrons are shared.
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An example of a compound containing a double bond is ethene (old name ethylene),
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which has the molecular formula C2H4 :
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H H
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C=C
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H H
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Each carbon atom requires a share in 4 electrons in order to complete its
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outer shell. Each H atom supplies one electron to pair with one of carbons
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electrons. As there are two H atoms connected to each C this uses up 2 of
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carbons 4 valency electrons. The only way both C atoms can obtain a complete
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outer shell is to now share both of their 2 remaining electrons with each other,
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so that each carbon atom gets a share in two electrons which originate from
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the neighbouring carbon atom.
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Nitrogen molecules are diatomic (contains two atoms, N2) and contain a triple
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bond between N atoms. Each N atom contains 5 electrons in the outermost shell,
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hence a share in 3 more is required to complete the octet and achieve an inert
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gas structure. If each N atom shares 3 of its 5 valency electrons with its
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neighbouring N atom, each achieves a stable octet. Each N atom thus retains
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two electrons (a lone pair) which fully belong to it, plus gets a share in six
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others (3 from itself, 3 from the other), thereby completing the octet around
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each atom.
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x x
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:N x x N: The N2 molecule, : represents a lone
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x x pair of electrons situated on each N.
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Double and triple bonds also occur between atoms of different types and are
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most important for the period two elements carbon, nitrogen and oxygen.
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For example, the carbon-oxygen double bond is very important in organic
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chemistry, where C=O is known as the _carbonyl_ group and is present in
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many important classes of compound eg. ketones, aldehydes, amides and esters.
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An oxygen atom contains six electrons in its outermost shell and therefore
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requires a share in two more to achieve an inert gas structure. A carbon atom
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requires a share in four electrons, therefore it shares two of its electrons
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with oxygen, which satisfies the requirements of oxygen. This still leaves
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the C atom two electrons short of the inert gas structure, which it achieves
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via bonding to other atoms. The nature of the other atoms attached to the
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carbonyl group will determine the reactivity and class of compound we have.
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Some examples are given below.
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Structural formula Class Name
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__________________ _____ ____
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H
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H-C-H
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C=O Ketone Propanone (acetone)
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H-C-H
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H
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CH3
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C=O Aldehyde Ethanal (acetaldehyde)
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H
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CH3
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C=O
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O-CH2-CH3 Ester Ethylacetate
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H
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C=O
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N-CH3 Amide Dimethylformamide
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CH3
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Common names shown in brackets.
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For the first compound in the table i drew the complete structural formula.
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However it is possible to shorten this slightly by writing :
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H
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-CH3 to represent -C-H
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H
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and
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H H
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-CH2-CH3 to represent -C-C-H
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H H
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The oxygen atom originally has 6 electrons in its outermost shell and shares
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two of these when forming two single covalent bonds (as in dimethylether) or
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one double bond (as in the above compounds). This leaves two lone pairs of
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electrons situated on oxygen, but these can usually be omitted when drawing
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the formulae for compounds.
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From the way we have discussed bonding so far, you may have expected a double
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covalent bond to be twice the strength of a single bond (if we consider the
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bonds to be between the same atoms). However, this is not the case and the
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double bond, although much stronger than a single bond, falls short of being
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twice the strength by a fair amount. To account for this we must go on another
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step in complexity and consider a more accurate model for the electronic
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structure of the atom. This i hope to do in another file if there is interest,
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but for the moment these basic ideas will suffice.
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The Coordinate Bond
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___________________
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So far you have seen that a single covalent bond consists of a pair of
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mutually shared electrons. One electron of the shared pair originated from
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one atom and the other electron from the other atom. However, there is a mode
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of bonding termed _coordinate_, or sometimes _dative_ in which the bond pair
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originates from the _same_ atom. To see how this is possible consider again
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the ammonia molecule, NH3. The nitrogen atom in ammonia has a lone pair of
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electrons. Even though the nitrogen atom has achieved its stable octet of
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outer electrons, it is still possible for further bonding to N to take place
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via the lone pair. For example, NH3 will react with a proton (H+, a hydrogen
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cation, formed by the removal of the single K electron from a H atom) to give:
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H
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| The positive charge now resides
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H-N->H on the N atom in NH4(+).
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H
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The lone pair from the N atom gives the newly attached H the inert gas config.
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of helium (K2) whilst at the same time it maintains the octet around N.
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Once formed, this coordinate bond is identical to that of a normal covalent
|
|
bond and all N-H bonds in NH4(+) are in fact identical. The positive charge
|
|
originally carried by H(+) is transferred to the nitrogen atom and the
|
|
resultant cation, NH4(+), is known as the ammonium ion.
|
|
|
|
|
|
The bond pair in molecules such as F2 and Cl2 is situated between identical
|
|
atoms, which are of course of identical electronegativity. Hence the electron
|
|
pair may be considered to be exactly in the middle of the two atoms. If however
|
|
the atoms which are linked by a covalent bond are of different electronegativity
|
|
then the electron pair of the bond will be drawn closer to the more
|
|
electronegative atom. This results in a _polarised_ bond in which the more
|
|
electronegative atom aquires a slight negative charge (because it hogs the
|
|
electrons) and the other a slight positive charge (beacuse the electrons are
|
|
being dragged away from it). This slight charge separation is represented by
|
|
d+ and d- (the greek letter delta). For example, consider a molecule A-B, in
|
|
which A is more electronegative than B. The bond becomes polarised in the
|
|
direction of A :
|
|
|
|
d- d+
|
|
A-B
|
|
|
|
|
|
The resulting partial positive and negative charges attract each other and
|
|
in fact strengthen the bond slightly. This electrostatic attraction is
|
|
no different to that found in ionic compounds, so the above bond could be
|
|
described as being partly ionic in character. In fact, if we kept increasing
|
|
the electronegativity of atom A and decreasing that of B the compound AB
|
|
would become increasingly more ionic as more and more negative charge
|
|
built up on atom A. When the difference in electronegativity between A and
|
|
B is great enough the compound will be ionic and consist of a lattice of
|
|
A- and B+ ions. Then there is the region between the extremes, where the
|
|
bond could be described as mainly covalent, but with some ionic character,
|
|
or mainly ionic, but with some covalent character. Methyl lithium (CH3Li) is an
|
|
example of a class of compounds known as the organometallics, and the bond
|
|
is about 40% ionic in character due to the extreme polarisation of the
|
|
C-Li bond :
|
|
|
|
H
|
|
d-| d+ In methyl lithium the C-Li bond is
|
|
H-C-Li extremely polarised.
|
|
|
|
|
H
|
|
|
|
Reagents such as MeLi (Me short for methyl, -CH3) are versatile reagents in
|
|
the synthesis of organic molecules, where the carbon skeleton of the molecule
|
|
usually has to be constructed from smaller molecules by a series of reactions.
|
|
|
|
|
|
|
|
Hydrogen Bonding
|
|
________________
|
|
|
|
Hydrogen bonding occurs in compounds which contain a hydrogen atom bonded to
|
|
a strongly electronegative element, most commonly oxygen and nitrogen. The
|
|
X-H bond (X=O,N etc) is polarised (d-)X-H(d+). The resultant d+ and d- charges
|
|
become attracted to the d- and d+ charges on another molecule of the compound,
|
|
with the result that a weak attractive force comes into play between the
|
|
molecules. If we consider water :
|
|
|
|
|
|
|
|
O.........H H Hydrogen bonding in water.
|
|
/ \ \ /
|
|
H H.........O ... = Hydrogen bond.
|
|
H . . .
|
|
\ . . .
|
|
O . O.........H
|
|
/ . / \ /
|
|
H H H.....O
|
|
\
|
|
H
|
|
|
|
|
|
Water has two H atoms bonded to one O atom and both of these H's can take
|
|
place in H bonding. The positively polarised H atoms in one molecule attract
|
|
the negatively polarised O atoms of other water molecules and a 3-D network
|
|
of hydrogen bonds is established. Hydrogen bonding is much weaker than either
|
|
covalent or ionic and H-bonds can be broken fairly readily. To break the H
|
|
bonds requires the input of energy (usually by heating). The high boiling
|
|
point of water is due to hydrogen bonding. The hydrogen bonds in water are
|
|
broken if the sample is heated enough (eg by boiling) and the water molecules,
|
|
with enough thermal energy that the H-bonds can no longer hold them together,
|
|
enter the gas phase.
|
|
|
|
Some examples of other types of compound which contain H-bonds are alcohols,
|
|
carboxylic acids, amines and amides.
|
|
|
|
|
|
Van der waals Forces of Attraction
|
|
__________________________________
|
|
|
|
This is an extremely weak force of attraction which operates between the
|
|
molecules in covalently bonded compounds. The size of the attractive force
|
|
generally increases with the weight of the molecule. A good illustration
|
|
of this principle is the trend in the boiling points of the alkanes, which
|
|
increase with increasing molecular mass. The alkanes are a family of organic
|
|
compounds which contain only carbon and hydrogen. Methane, CH4, is the lightest
|
|
of the alkanes and as such the V.D.W forces of attraction between its molecules
|
|
are extremely weak, hence methane is a gas at room temperature. For the next
|
|
heavier alkanes ethane (CH3CH3), propane (CH3CH2CH3) and butane (CH3CH2CH2CH3)
|
|
the V.D.W forces do increase, but not enough to allow the alkane to be a liquid
|
|
at room temperature. However, the next members pentane and hexane are fairly
|
|
volatile liquids at room temperature. The boiling point continues to increase
|
|
with increasing molecular weight. When the molecular weight is high enough,
|
|
the V.D.W forces between the molecules will have increased enough so that the
|
|
alkane becomes a low melting point solid (as in candle wax). Hence most
|
|
covalent compounds are either gases, liquids or low melting point solids
|
|
(there is an exception to this where in some cases infinite 3-D covalent
|
|
structures are formed, as opposed to discrete molecules, as in diamond and
|
|
silica, in these cases the boiling points are abnormally high).
|
|
|
|
|
|
Shapes of Simple Covalent Molecules - VSEPR Theory
|
|
__________________________________________________
|
|
|
|
The shapes of most simple covalent molecules can be predicted by using the
|
|
valence shell electron pair repulsion theory. This theory states that the
|
|
shape of a molecule is related to the number of electron pairs (bond pairs or
|
|
lone pairs) in the outer shell of the central atom. It is assumed that the
|
|
electron pairs arrange themselves to be as far apart as possible in order to
|
|
minimise the repulsive forces between them (negative charges repel). If the
|
|
distribution of these pairs can be predicted then so can the shape and bond
|
|
angle.
|
|
|
|
Consider the structure of a gaseous molecule of beryllium fluoride BeF2.
|
|
In this molecule the central Be atom forms two single covalent bonds, one bond
|
|
to each fluorine atom. There are therefore 2 bonding pairs of electrons in the
|
|
valence shell of the Be atom in BeF2. These 2 pairs will arrange themselves to
|
|
be as far apart as possible - and this is 180 degrees to each other. The BeF2
|
|
molecule is therefore linear, with a F-Be-F bond angle of 180 degrees. You
|
|
may have noticed that the central Be atom has only 4 electrons in its outermost
|
|
shell i.e. it does not have a complete inert gas structure. The molecule is
|
|
described as being electron deficient.
|
|
|
|
A molecule of boron trifluoride, BF3, has a central B atom covalently bonded to
|
|
three fluorine atoms by single covalent bonds. The three bond pairs arrange
|
|
themselves so that repulsion is at a minimum - and this is in a plane triangular
|
|
shape, with the F-B-F bond angles equal to 120 degrees. The fluorine atoms
|
|
occupy the corners of an equalateral triangle, with the boron atom in the
|
|
middle.
|
|
|
|
In methane, CH4, there are four bond pairs of electrons around the central
|
|
carbon atom. The repulsion is at a minimum if the bond pairs arrange themselves
|
|
tetrahedrally around the C atom i.e. all H-C-H bond angles are 109 degrees 28
|
|
minutes. The hydrogen atoms then occupy the corners of a regular tetrahedron
|
|
and the CH4 molecule is described as tetrahedral.
|
|
|
|
Ammonia, NH3, has four pairs of electrons around the central N atom. These
|
|
comprise three bonding pairs (one bond to each H atom) and a lone pair.
|
|
Because the lone pair is not shared with any other atom it is pulled closer
|
|
to the N atom than are the bond pairs. This results in the lone pair being
|
|
more replusive than a bond pair, so the order of repulsion between types is
|
|
|
|
Lone pair - Lone pair > Lone pair - Bond pair > Bond pair - Bond pair
|
|
|
|
In ammonia the 4 pairs are again tetrahedrally distributed, with one of the
|
|
corners of the tetrahedron occupied by the lone pair. This gives the molecule
|
|
a pyramidal shape:
|
|
"
|
|
| Molecule of ammonia.
|
|
N
|
|
/|\
|
|
H H H
|
|
|
|
The extra repulsion of the lone pair pushes the bonding pairs closer together
|
|
and thus reduces the H-N-H bond angle from the expected 109 degrees for a
|
|
regular tetrahedron, to ##### degrees. It is hard to draw 3D diagrams on this
|
|
terminal - the three H's are not in the plane of the screen! The N forms the
|
|
apex of a pyramid.
|
|
|
|
Water has four pairs of electrons around the central oxygen atom. These
|
|
comprise two bond pairs and two lone pairs. Again the distribution of the pairs
|
|
is roughly tetrahedral, but this time two of the corners of the tetrahedron
|
|
are occupied by lone pairs. Because there are two lone pairs which provide
|
|
extra repulsion, the H-O-H bond angle is reduced to #### degrees. The molecule
|
|
is V-shaped:
|
|
O
|
|
/ \
|
|
H H
|
|
|
|
Molecules with five bond pairs (and no lone pairs) usually adopt a trigonal
|
|
bipyramid structure eg PCl5 (in the gas phase):
|
|
|
|
* Cl
|
|
\|
|
|
P-*
|
|
/|
|
|
* Cl
|
|
|
|
Three of the Cl atoms are in the same plane and form an equalateral triangle.
|
|
These i have represented by a * instead of a Cl. The Cl-P-Cl bond angle (*-P-*)
|
|
is 120 degrees. The other two chlorine atoms are arranged 180 degrees to each
|
|
other and at 90 degrees to the plane of the triangle formed by the three Cl's
|
|
marked *. Three different Cl-P-Cl bond angles are therefore present.
|
|
|
|
|
|
Dalamar.
|
|
|
|
-------------------------------------------------------------------------
|
|
To find out more about the anon service, send mail to help@anon.penet.fi.
|
|
Due to the double-blind, any mail replies to this message will be anonymized,
|
|
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|
|
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|
|
|
|
=============================================================================
|
|
|
|
Message-ID: <104313Z09071994@anon.penet.fi>
|
|
Newsgroups: alt.drugs
|
|
From: an58264@anon.penet.fi (Dalamar)
|
|
Date: Sat, 9 Jul 1994 10:39:46 UTC
|
|
Subject: CHEMISTRY: Bonding and Structure [missing bond angles]
|
|
|
|
|
|
Whoops !
|
|
|
|
When i was writing the file i left the two bond angles for NH3 and H20 blank
|
|
because i couldn't remember the exact figures. I meant to go and look them up
|
|
but it must have slipped my mind. Anyway, here they are :
|
|
|
|
|
|
NH3 = 106 degrees, 45 minutes
|
|
|
|
H20 = 104 degrees, 27 minutes
|
|
|
|
|
|
|
|
Dalamar.
|
|
|
|
-------------------------------------------------------------------------
|
|
To find out more about the anon service, send mail to help@anon.penet.fi.
|
|
Due to the double-blind, any mail replies to this message will be anonymized,
|
|
and an anonymous id will be allocated automatically. You have been warned.
|
|
Please report any problems, inappropriate use etc. to admin@anon.penet.fi.
|
|
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|
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