Introduction to bonding ATTAINMENT OF A STABLE CONFIGURATION How do atoms combine to form molecules and why do atoms form bonds? A molecule will only be formed if it 1s more stable, and has & lower energy, than the individual atoms To understand what 1s happening mn terms of electrome structure, con sider first the Group 18 elements These comprisethe noble gases, helum, neon, argon, krypton, xenon and radon, which are noteworthy for their chemucal mertress Atoms of the nable gases do act normally react with any other atoms, and their molecules are monatomic, 1 e contain only one atom The fack of reactivity 1s because the atoms already have 2 [ow energy, and it cannot be lowered further by forming compounds The low energy of the noble gases 1s associated with theit having a complete outet shell of electrons This is often called a noble gas siructure, and st is an exceptionally stable arrangement of electrons Normally only clectrons in the outermost shell of aa atom are involved in formmg bands, and by forming bonds each atom acquires a stable electron configuration The most stable electronic arrangement 1s a noble gas structure, and many molecules have this arrangement However, less Stable arrangements than this are commonly attained by transition elements TYPES OF BONDS Atoms may attain a stable electronic configuration in three different ways by losing electrons, by gaining electrons, or by sharing electrons Elements may be divided into 1 Electroposinve elements, whose atoms give up one or more electrons farrly readily 2 Electronegative elements, which will accept electrons 3° Elements which have {tle tendency to lose or gain electrons Three different types of bond may be formed, depending on the electropositive of clectronegative chatacter of the atoms involvedTRANSITIONS BETWEEN THE MAIN TYPES OF BONDING Electropositive element + Ionic bond Electronegative element Electronegative element + Covalent bond Electronegative element Electropositive element + Metallic bond Electropositive element lonic bonding involves the complete transfer of one or more electrons from one atom to another. Covalent bonding involves the sharing of a pair of electrons between two atoms, and in metallic bonding the valency electrons are free to move throughout the whole crystal. These types of bonds are idealized or extreme representations, and though one type generally predominates, in most substances the bond type is somewhere between these extreme forms. For example, lithium chloride is considered to be an ionic compound, but it is soluble in alcohol, which Suggests that it also possesses a small amount of covalent character. If the three extreme bond types are placed at the corners of a triangle, then compounds with bonds predominantly of one type will be represented as points near the corners. Compounds with bonds intermediate between two types will occur along an edge of the triangle, whilst compounds with bonds showing some characteristics of all three types are shown as points inside the triangle, Metallic ti 7X Ag Na,Bi / \ Sn Na3Sb / As Na,As Te NasP Ss Na3N / “\ 12 - CIF ~OF 2-NF3-CCi,- BF, -BeF, + Na,O Fa~ iF; — SFg — PF, ~ SIF. — AlFy — MgF2 ~ CsF Covalent Figure 2.1 Ty i i hon ding, (Rowe illustrating the transitions between ionic, covalent and metallic Produced from Chemical Constitution. by J.A.A. Ketelaar, Elsevier. } tonic32] INTRODUCTION TO BONDING J ‘TRANSITIONS BETWEEN THE MAIN TYPES OF BONDING Few bonds are purely tonic covalent or metallic Most are intermediate between the three main types and show some properties of at least two and sometimes of all three types lonic bonds Tonic bonds are formed when electropositive elements react with electro negative clements Consider the tonic compound sodium chtonde A sodium atom has the electrome configuration 1s? 2s? 2p* 3s' The first and second shells of electrons are full but the third shelf contans only one efectron When this atom reacts it will do so in such 2 way that tt attains a stable electron configuration The noble gases have a stable electron arrangement 1nd the nearest noble gas to sodium ts neon whose configuration 1s 1s? 2s? 2p* If the sodium atom can lose one electron from sts outer shell «ct will attain this configuration and in doing so the sodium acquites a net charge of +1 andis calfed a sodium 10n Na* The positive charge arises because the nucleus contains [1 protons each with a positive charge but there are now only {6 electrons Sodium atoms tend to fose an electron in this way When they are supplied with energy and so sodium ss an electroposinve element Na -» Na* + electron sedum at sodum on Chiorine atoms have the electronic configuration Is” 2s” 2p* 35” 3p* They are only one electron short of the stable noble gas configuration of argon 1s 2s” 2p* 3s" 3p* and when chlorine atoms react they gain an electron Thus chlorine 1s an electronegative element a + electron — Cl cM ng at m chlo dean Through gaining an electron an electrically neutral chlorine atom becomes aachloride ton with a net charge of -1 When sodium and chlorine react together the outer electron of the sodium atoms 1s transferred to the chlorine atoms to produce sodium tons Na* and chionde tons Cl Electrostatic attraction between the positive and negative tons holds the ions together in a crystal lattice The process 15 energetically favournble as bath sorts of atoms attain the stable noble gas configuration and sodium chloride Na*C) 15 formed readily This may be allustrated diagrammatically im a Lewis diagram showing the outer electrons as dots Na+ C= Nal" +[o] ‘ust um stems chlerne ay axtum yon chloride Ko| TRANSITIONS BETWEEN THE MAIN TYPES OF BONDING The formation of calcium chloride CaCl, may be considered in a similar way. Ca atoms have two electrons in their outer shell. Ca is an electropositive element, so each Ca atom loses two electrons to two Cl atoms, forming a calcium ion Ca?* and two chloride ions Cl~. Showing the outer electrons only, this may be represented as follows: a: Fe] Ca: + — [Caf + -Cc: : Cc) | calcium atom chlorine atoms calcium ion chloride inane Covalent bonds When two electronegative atoms react together, both atoms have a tendency to gain electrons, but neither atom has any tendency to lose electrons. In such cases the atoms share electrons so as to attain a loble gas configuration. First consider diagrammatically how two chlorine atoms Cl react to form a chiorine molecule Cl, (only the outer electrons are shown in the following diagrams): :A.+°C:> :ca:ca: chlorine atoms chlorine molecule Each chlorine atom gives a share of one of its electrons to the other atom. A pair of electrons is shared equally between both atoms, and each atom now has eight electrons in its outer shell (a stable octet) -— the noble gas Structure of argon. In this electron dot picture (Lewis structure), the Shared electron pair is shown as two dots between the atoms Cl : Cl. In the valence bond representation, these dots are replaced by a line, which Tepresents a bond CI—Cl. in a similar way a molecule of tetrachloromethane CCl, is made up of one carbon and four chlorine atoms: ci Coad Joa:c:a cl forms eon atom is four electrons short of the noble gas Structure, so it each fonn one bn ane the chlorine atoms are one electron short, so they all four chin ond. By Sharing electrons in this way, both the carbon and mine atoms attain a noble gas structure. It must be emphasized J (33B4 INTRODUCTION TO BONDING that although 1t 1s possible to build up molecules m this way in order to understand their electronic structures, 1 does not fojlow that the atoms will react together directly In this case, carbon and chlorme do not react directly, and tetrachloromethane ts made by indirect reactions A molecule of ammoma NHs 1s made up of one nitrogen and three hydrogen atoms N +3}H }+H NH H The nitrogen atom 1s three electrons short of a noble gas structure, and the hydrogen atoms are one electron short of a noble gas structure Nitrogen forms three bonds, and the hydrogen atoms one bond each, so all four atoms attain a stable configuration One pair of electrons on the N atom is not involved in bond formatyon and this 1s called a lone parr of electrons Other examples of covalent bonds include water (with two covalent bonds and two lone pants of electrons), and hydrogen fluonde (one covalent bond and three lone pairs) HO H F H Oxidanon numbers ‘The oxidation number of an element in a covalent compound 1s calculated by assigning shared clectrons to the more electronegative element, and then counting the theoretical charge left on each atom (Electronegativity 1s described in Chapter 6) An alternative approach 1s to break up (theoretically) the molecule by removing all the atoms as ions, and counting the charge left on the central atom It must be emphasized that molecules are not really broken, nor electrons really moved. For example in HO, removal of two H* leaves a charge of —2 on the oxygen atom $0 the oxidation state of O on HzO is (—11) Similarly tn HS the oxidauon state of S 1s (II), m F,O the oxidation state of O ss (+11), in SF, the oxdation state of S 1s (+1V) whilst in SF, the oxidation state of $ 1s (VD The concept of oxidation numbers works equally well with 1onic compounds and im CrCl; the Cr atom has an oxidation state of (+121) and at forms Cr** tons Similarly m CrCl, Crhas the oxsdauion state (+11) and exists as Cr?* rons Coordinate bonds A covalent bond results from the sharing of a parr of electrons between two atoms where cach atom contributes one electron to the bond It 1s alsoTRANSITIONS BETWEEN THE MAIN TYPES OF BONDING possible to have an electron pair bond where both electrons originate from oue atom and none from the other. Such bonds are called coordinate bonds or dative bonds. Since, in coordinate bonds, two electrons are shared by two atoms, they differ from normal covalent bonds only in the way they are formed, and once formed they are identical to normal covalent bonds. Even though the ammonia molecule has a stable electron configuration, it can react with a hydrogen ion H* by donating a share in the lone pair of electrons, forming the ammonium ion NH7: H H * H }* H:N:+[HJ* > j}H:N:H] or|H—NoH H H H Covalent bonds are usually shown as straight lines joining the two atoms, and coordinate bonds as arrows indicating which atom is donating the electrons. Similarly ammonia may donate its lone pair to boron trifluoride, and by this means the boron atom attains a share in eight electrons: HF H F | H:N:+B:F ~+ H~—N->B—F | | H F H F In a similar way, a molecule of BF, can form a coordinate bond by accepting a share in a lone pair from a F~ ion. F F ~ oe . | : F ] +B:F - |F>B—F F F There are many other examples, including: PCI, + CIT > [PCI,]~ SbFs + F~ — [SbF,]~ Double and triple bonds Sometimes mor four electrons a 's called a dou bonds, and thi e than two electrons are shared between a Pair of atoms. If Te shared, then there are two bonds, and this arrangement ble bond. If six electrons are shared then there are three S Is called a triple bond: