Chapter 4 part 2 4.5. OTHER TYPES OF BONDING 4.5.1.

Hydrogen bonds: Hydrogen bonds are well defined by a description of the hydrogen bonds in hydrogen fluoride (FIG. 4.5).

4.5. . Van der Waals bonds are !ery wea" forces of electrostatic attraction a#ongst instantaneous dipoles and induced dipoles. $t a gi!en #o#ent in ti#e% the electron cloud surrounding e!en an inert gas ato# #ay not be perfectly sy##etrical. &hus one side will carry a relati!e positi!e charge and the other a relati!e negati!e charge. &he separation of charge (d !ole) can be al#ost negligible in s#all ato#s such as heliu#. In addition to these instantaneous dipoles% there are dipoles induced by the original dipoles. 'ince the dipoles are !ery s#all% the forces which e(ist between the# are also !ery s#all. )!en at low te#peratures% the rando# #otion of group *III ato#s is

!igorous enough to "eep the# gaseous. +oreo!er% on collision% repulsion between li"e charges is ,ust as li"ely to occur as attraction between opposite charges. Howe!er% as e(tre#ely low te#peratures are reached% the rando# #otion is not enough to brea" !an der -aals attractions #ore often than they occur. )!entually% at low enough te#peratures% the gas #ay li.uefy% and the li.uid #ay then e!en solidify. In energy ter#s% the "inetic energy is less than the bonding energy. &he larger an ato# or #olecule% the easier it is for dipoles to e(ist. In large ato#s this is because the outer electrons are a long way fro# the control of the nucleus. /elati!ely si#ple large #olecules (e.g. iodine) #ay solidify e!en at roo# te#perature. In contrast% heliu# #ust be reduced to 40% and a pressure of 112 at#ospheres #ust be applied% in order for solidification to occur. *an der -aals forces are particularly i#portant in deter#ining the shapes which #acro#olecules such as proteins adopt (section 5. .5.). Here% the large nu#ber of bonds co#pensates for their e(tre#e wea"ness. &his #ay also be the case between !ery large #olecules. 3ote that in 43$% large nu#bers of hydrogen bonds are the i#portant bonds holding the two strands together (section 5.4.5.). 4.". BONDING #H$R$#TERISTI#S 4.5.1. T%e &a n 'y!e o( bond ng has effects on properties% as su##arised in &$67). 4.1.

&he fact that ionic co#pounds ha!e high #elting and boiling points whereas co!alent co#pounds ha!e low #elting and boiling points does not indicate that ionic bonds are stronger than co!alent bonds. &he high #elting and boiling points of ionic co#pounds do indicate that ionic bonds are strong i.e. the te#perature #ust be high before ionic #otion is !igorous enough to o!erco#e the electrostatic forces of attraction. Howe!er% co!alent bonds are also generally !ery strong% but it is not these which brea" when s#all #olecular co#pounds #elt or boil. It is e(tre#ely wea" !an der -aals forces between one #olecule and another which brea". 4.). INTER*EDI$TE TYPES OF BONDING 4.8.1. T%e '%ree &a n 'y!es of bonding% electro!alent% #etallic% and co!alent are e(tre#e cases. $s often as not% bonding is inter#ediate between two types. 4.8. . Ele+'ro,alen' ,s. +o,alen': &here is an initial proble# here of deciding whether to treat the bonding as ionic with co!alent character or co!alent with ionic character. &his #ust be ,udged fro# an o!erall assess#ent of properties. For e(a#ple% any co#pound which conducts electricity in the #olten state is #ore li"ely to be ,udged as principally ionic than it is to be ,udged as principally co!alent% and !ice !ersa. - Ion + bond ng . '% +o,alen' +%ara+'er: -hen two types of ion co#e together to for# a co#pound% there is li"ely to be a high degree of co!alent character when: First% the positi!e ion is: a) s#all ...................................b) highly charged 'econd% the negati!e ion is: a) large ........................................b) highly charged (&hese e#pirical rules are "nown as Fa,an9s rules.) It is predicatable that a s#all% highly charged positi!e ion will ha!e a high surface charge density% and will tend to attract electrons away fro# the negati!e ion into a co!alent bond. It is also predictable that it will be easiest to re#o!e electrons fro# negati!e ions when those electrons are a long way fro# the negati!e ion9s nucleus% and when there is a large nu#ber of :e(tra: electrons in the outer shell.

- #o,alen' bond ng . '% on + +%ara+'er: -hen a largely co!alent bond for#s between ele#ents of differing electronegati!ity (#ost cases)% the electron pair will not be shared e.ually. &he #ore electronegati!e ele#ent will ha!e a greater share of the bonding pair% as in the case of H;l #olecules:

If it see#s li"e fantasy to consider this #olecular gas as partially ionic% re#e#ber that it dissol!es in water to produce hydrated H < and ;l= ions. 'o#eti#es the polarity of a #olecule will be enhanced by its shape and the e(istence of lone pairs:

&he assy#etric a##onia #olecule is polar. $part fro# discrete polar #olecules% #olecular solids #ay also e(hibit ionic character. In fact% the #ere e(istence of co!alent #olecules in a solid lattice is a step towards ionic character: the !an der -aals bonding between #olecules is beco#ing less distinguishable fro# the co!alent bonding within the #olecules (e.g. section 14.2.1.). 4.8.2. #o,alen' ,s. &e'all + bond ng: &his is #ost relel!ant to the case of pure ele#ents and is well illustrated by changes down group I* (section 18. .1) and group *II (section 15. .1.) and by changes across the period fro# sodiu# to chlorine. -e shall discuss the changes across a period here. 'odiu# (7H') is electropositi!e and for#s clear=cut #etallic bonding. ;hlorine (/H') is electronegati!e and for#s diato#ic #olecules with a precise co!alent bond between the two ato#s.

Fro# sodiu# to alu#iniu#% the increasing effecti!e nuclear charge (as well as the increasing nu#ber of electrons contributed by each ato# to the #etallic bonding orbital) causes the #etallic bonding to beco#e stronger. (3ote that this is not the sa#e as saying the bonding beco#es beco#e #ore #etallic.) 6y silicon% the effecti!e nuclear charge is high enough to hold the bonding electrons in fairly concentrated regions of electron density on the a(es between the nuclei i.e. the bonds are #ore co!alent than #etallic% but silicon still has a lattice structure #ore co#parable with a #etal than with the discrete #olecules nor#ally associated with co!alent bonding. +oreo!er% silicon has a #etallic lustre% suggesting that the bonding electrons are diffuse enough to reflect light. 'o#e of silicon9s se#i=conducti!e properties #ay also be considered as inter#ediate between #etallic and co!alent properties. &he higher effecti!e nuclear charges of phosphorus and sulphur result in e!en #ore coa!lent character. 4iscrete #olecules are for#ed% > 4 and '?% but !an der -aals forces between one #olecule and another are strong enough for both ele#ents to be solids at roo# te#perature. 4./. PREDI#TING THE N0*BER OF BONDS 4.?.1. Ha, ng !red +'ed the type of bonding% it is necessary to predict the nu#ber of bonds (charge in the case of ions). 4.?. . T%e o+'e' (able: In its least contro!ersial for# the octet :rule: obser!es that ato#s often end up with eight outer electrons when they for# bonds. In its #ost contro!ersial for# it suggests that ato#s for# bonds in order to achie!e this configuration. &he configuration ac.uires the status of :stable octet: which is attributed with #agical properties resulting fro# its si#ilarity to the outer electron configuration of the :noble: gas ato#s. >erhaps it is the wishy=washy use of stability as an e(planation which has allowed the continuation of the #yth. In #ore cases than this% use of the word :stable: is an atte#pt to #a"e :low energy: sound li"e a co#plete e(planation. &he facts are e!en #ore disturbing. For one thing% in energy ter#s the octet is usually less stable than the electron configuration of the parent ato#. &his is indicated by the fact that e!en group I #etal ato#s (which are a#ongst the #ost able to lose electrons and for# positi!e ions with an outer octet) re.uire energy to re#o!e the outer electron. It is true that ;l=% with its outer octet% is #ore :stable: than the parent ato# (electron affinities are often negati!e) but this is not because for#ing negati!e ions achie!es the octet.

&his is clearly illustrated by o(ygen. $n @ = ion is #ore :stable: than an o(ygen ato#. &he first electron affinity is negati!e i.e. the ion has less energy than the parent ato# and energy is gi!en out as heat when it for#s. Howe!er% when @ = goes on to achie!e the octet by for#ing @ =% energy is re.uired. )le#ents which for# negati!e ions are ele#ents with high effecti!e nuclear charges% and this is :why: first electron affinities can be negati!e. Howe!er% when a second electron is added to @=% it is repelled by the negati!e charge of the ion and #ust be added to a s#all shell which already contains se!en% negati!ely charged% electrons. 3ote that we ha!e found it necessary to e(plain energy changes in ter#s of electrostatic forces. 4.?.2. R1bb ng ' n: In addition to all this% there are plenty of cases where bonding does not result in an outer octet: - *ore '%an '%e o+'e': a) )lectro!alent: Fe2< has 12 outer ..........................................electrons in Fe ('@4)2 ......................................b) ;o!alent: 'ulphur has 1 outer ..........................................electrons in 'F5 - Fe.er '%an '%e o+'e': a) )lectro!alent: >b < has outer ............................................electrons in >b'@4 ........................................b) ;o!alent: $l has 5 outer electrons ............................................in $l;l2 &he situation is #ore in!ol!ed than the octet rule i#plies. &here are far #ore e!ents occurring than #erely the for#ation% or otherwise% of octets. It is con!enient to tac"le the proble# in ter#s of a #ore detailed loo" at energy changes% and to refer to the electrostatic forces in!ol!ed in order to understand the#. 4.?.4. Pred +' ng '%e +%arge on a !os ' ,e on: @b!iously this step co#es after deciding that a co#pound is electro!alent and after deciding which ele#ent constitutes the positi!e ion. - T%e +%arge on a !os ' ,e on is e.ual to the nu#ber of electrons lost by the parent ato#. $n ato# is unli"ely to lose #ore electrons than it has in the outer shell because the ne(t shell is closer to (:and less screened fro#:) the attraction of the nucleus. $n ato# is unli"ely to lose fewer electrons than it has present in the outer shell. &his is because co#plete loss of the outer shell electrons not only #a"es the ion

#ore highly charged% but also #a"es it #uch s#aller. &he resultant ion will therfore Afor# a #uch stronger lattice (in a.ueous solution% it will be #uch #ore strongly hydrated). -ith respect to calciu#% try to picture the e!ents and i#agine the changing electrostatic forces when calciu# ato#s react with o(ygen ato#s. &hen try to i#agine the e!en #ore co#ple( e!ents when calciu# #etal reacts with o(ygen gas. (AIn energy ter#s% the #uch higher lattice energy co#pensates for the e(tra ionisation energies.) - E2+e!' ons: Bnli"e the octet rule% this approach pro!ides a basis for understanding e(ceptions. For e(a#ple% ele#ents at the botto# of group I* can for# < ions as well as the e(pected 4< ions (section 18.2. .iii). &he beha!iour of d=bloc" ele#ents can also be understood. &hey can lose penulti#ate shell electrons as well as outer electrons because there is little difference in the strength with which their penulti#ate d=electrons and outer s= electrons are held by the nucleus (section .4.2.). 4.?.5. Pred +' ng +%arge on a nega' ,e on: -hen an electronegati!e ato# gains electrons to for# negati!e ions it fills any singly occupied orbitals in its outer shell. It is unli"ely to gain #ore than this nu#ber of electrons% since this would in!ol!e attracting electrons into a shell further (:and #ore screened fro#:) the attraction of the nucleus. It is unli"ely to gain fewer electrons% because filling the singly occupied orbitals increases the charge but results in a relati!ely s#all increase in the o!erall siCe of the ion. &he resultant ion will therefore Afor# a stronger lattice than an ion which still has a singly occupied orbital. -ith respect to o(ygen% try to picture the e!ents and i#agine the changing electrostatic forces when calciu# ato#s react with o(ygen ato#s. &hen try to i#agine the e!en #ore co#ple( e!ents when calciu# #etal react with o(ygen gas. (A In energy ter#s% the e(tra lattice energy co#pensates for the e(tra electron affinity.) 4.?.5. Pred +' ng '%e n1&ber o( +o,alen' bonds : - #o,alen' bonds3 @b!iously% predicting the nu#ber of co!alent bonds co#es after deciding that the bonding is co!alent. ;o!alent bonds are usually for#ed by

the o!erlap of singly occupied ato#ic orbitals% and the nu#ber of singly occupied orbitals in ato# gi!es a rough indication of the nu#ber of bonds it will for#. - Ele+'ron !ro&o' on: &here are% as you will recall% co#plications. For e(a#ple% carbon in its :ground state: has two singly occupied orbitals:

. Howe!er% carbon al#ost e(clusi!ely for#s four bonds. &his is described in ter#s of a #odel in which one of the s electrons is pro#oted into the !acant p orbital% gi!ing it four singly occupied orbitals:

&he ad!antage of for#ing 4 bonds can be seen by considering #ethane. In each ;=H bond the carbon and hydrogen nuclei are attracted to the high electron density of a bonding pair of electrons. &his attraction is greater than the total attraction of a carbon nucleus for one of its outer electrons plus that of a hydrogen nucleus for its outer electron in an H #olecule. In other words% the for#ation of two e(tra bonds outweighs the ad!antages of lea!ing carbon9s s= electrons paired and closer to the nucleus than they would be in a p=orbital. +oreo!er% the electrons actually enter bonding orbitals rather than p=orbitals% as we shall see in section 4.?. In energy ter#s% the two e(tra bond energies #ore than co#pensate for any pro#otion energy% and the H=H bond energy (c.f. section 18.2.1.ii.). - d4orb 'als: fro# the third period onwards% d=orbitals are a!ailable for electron pro#otion. &hus sulphur can for# % 4% or 5 bonds:

In this electron pro#otion #odel% the nu#ber of bonds for#ed is dependent on the nu#ber of electrons pro#oted. &his in turn depends on:

a) &he siCes of the bonding ato#s b) &he effecti!e nuclear charges of the bonding ato#s. &hese can be deduced fro# the positions of the ele#ents in the periodic table. +oreo!er% they affect two #ain aspects of co!alent bonding which the#sel!es ha!e a bearing on the nu#ber of bonds for#ed: a) First they affect the strengths of the bonds for#ed: then it can be predicted that the stronger the bonds% the larger the nu#ber li"ely to for#. b) 'econd% they affect the a#ount of space a!ailable for bond for#ation: then it can be predicted that the larger the bonding ato#s relati!e to the central ato#% the s#aller the nu#ber of bonds li"ely to for#% owing to lac" of space. &hus% referring bac" to sulphur% this ele#ent for#s 'F 5 but not ';l5. &his is predicatble for two reasons: First% fluorine9s nucleus is closer to (:and less screened fro#:) the bonding electrons than is chlorine9s nucleus. Fluorine therefore for#s stronger bonds than chlorine with sulphur. 'econd% chlorine9s larger siCe #eans that there is less roo# for 5 of its ato#s to fit around the s#all central sulphur ato# (FIG. 4.18.) Dou are li"ely to de!elop a feel for this "ind of reasoning only after considering a good nu#ber of e(a#ples. 3ote also: c) +ultiple bonding reduces the nu#ber of bonded ato#s re.uired to for# the higher o(idation states. ,- Da' ,e +o,alen' bonds: a final co#plication is that orbitals containing pairs of electrons #ay be in!ol!ed in dati!e co!alent bond for#ation by o!erlap with !acant ato#ic orbitals. +oreo!er% singly occupied orbitals #ay beco#e a!ailable for dati!e bond for#ation by spin=pairing:

It is possible to predict the li"lihood of dati!e bond for#ation fro# its strength and the a#ount of roo# a!ailable% and thus fro# siCes and effecti!e nuclear charges of the bonding ato#s. Hence (ulti#ately) the prediction can be #ade fro# the

positions of the bonding ele#ents in the periodic table. $gain you will de!elop a feel for this after considering a large nu#ber of cases. In the 3 @4 #olecule cited abo!e% it is found that in practice all the 3=@ bonds are e.ui!alent. &his e#phasises the fact that we are using a only partially correct #odel in order to #a"e predictions. &he #odel is de!eloped by considering one #ore piece of bonding theory% %ybr d sa' on. 4.5. HYBRIDIS$TION 4.E.1. T%e s%a!es of ato#ic orbitals co#e fro# the solution of co#ple( wa!e e.uations. 'uch calculations also allow shapes to be assigned to bonding orbitals% and they rely hea!ily on energy considerations. &he wa!e e.uations are si#plified by considering only the predicted shapes of orbitals which ato#s could theoretically use to for# bonds. Fuantu# #echanists can actually calculate the space around a nucleus in which an electron will #ost probably occur (FIG. .2.). &he shape is a direct function of the orbital9s energy% and this can change if hybridisation is included in the .uantu# #echanical calculations. 4espite the useful outco#e of these calculations% it is not wise to be generally bullied by #athe#eticians. $ cynic #ight say that they resort to #athe#atical #odels because they ha!e as #uch difficulty understanding reality as we ha!e understanding the#. +athe#atical #odels #ust% as they are here% be related to reality. &he calculated shape of an orbital is !ery useful for de!eloping the #odels we use to describe ato#s and #olecules. 4.E. . W%y .e need '%e +on+e!' o( %ybr ds : )!en when carbon is described as ha!ing pro#oted its s electron into the !acant p orbital% it is not in an appropriate state to for# bonds% according to our e(isting #odels. &his is despite ha!ing four singly occupied orbitals. $ccording to our e(isting #odel% the four orbitals are not a con!enient shape% nor are they con!eniently arranged% to o!erlap with other ato#ic orbitals (FIG. 4.5.)

Howe!er% orbital shape is calculated as a function of energy. If the energy of an orbital were different fro# that considered as nor#al in a free ato#% we would conse.uently predict a different shape. &he energies of these orbitals would be different fro# nor#al if the distribution of energies a#ongst the orbitals were different fro# nor#al. +oreo!er% the distribution of energy would be different fro# nor#al if the s orbital were e.ui!alent in energy to one or #ore of the p=orbitals. $s a predicti!e tool% it is suggested that this e.ualisation of energy does e(ist. It is "nown as hybridisation% and associated calculations describe so#e #uch #ore con!eniently shaped (sp hybrid) orbitals (FIG. 4.8.).

&here are three possibilities: s!67 s!87 and s!9 %ybr d sa' on.

4.E.2. s!9 %ybr d sa' on: In this case the s=orbital is considered as e.ui!alent in energy to all three p=orbitals% gi!ing four sp 2 hybrid orbitals (FIG. 4.?.).

&he four orbitals point to the four corners of a 'e'ra%edron. 4.E.4. s!8 %ybr d sa' on: In this case the s=orbital is considered as e.ui!alent in energy to two of the p=orbitlas% gi!ing three sp hybrids% and lea!ing one p=orbital with a higher energy (FIG. 4.E.).

&he three sp hybrids point to the three corners of an e:1 la'eral 'r angle. 4.E.5. s!6 %ybr d sa' on: In this case the s=orbital is considered as e.ui!alent in energy to one of the p=orbitals% gi!ing two sp 1 hybrids% and lea!ing two p=orbitals with a higher energy% but with the sa#e energy as each other (FIG. 4.11).

&he sp1 orbitals are arranged l nearly. 4.E.5. s!9 %ybr ds n &e'%ane (FIG. 4.11.):

In an s=bond% the electron density is concentrated along the a(is between the centres of the two bonded ato#s. 4.E.8. s!8 %ybr ds n e'%ane (FIG. 4.1 ):

4.E.?. s!8 %ybr ds n b1'a46794d ene (FIG. 4.12.):

)lectrons are said to be delo+al sed when they are not confined to the positions indicated in a si#ple bonding diagra#% but are spread out by% for e(a#ple% p= orbital and p=bonding syste# o!erlap. 4.E.E. s!8 %ybr ds n ben;ene (FIG. 4.14.):

4.E.11. s!6 %ybr ds n e'%yne (FIG. 4.15.):

4.6<. SH$PES OF *O=E#0=ES

4.11.1. Hybr d sa' on '%eory allows the shapes of #olecules to be predicted. 'hape #ay also be predicted by re#e#bering that electrons in one bond will repel electrons in another. &he repulsi!e effect of #ultiple bonds will be greater than the repulsi!e effect of single bonds. $lso% lone pairs of electrons will repel electrons in bonds% and repel other lone pairs% as well. 7one pairs e(ert a greater repulsi!e force e!en than #ultiple bonds. &hus the shape of a #olecule will tend to achie!e #a(i#u# separation of bonds and lone pairs% ta"ing into consideration the relati!e strengths of the repulsi!e forces. &hese are su##arised as decreasing in the order: lone pair G #ultiple bond G single bond. (&his is a su##ary of% so=called% 'idgwic"=>owell &heory). 'o#e e(a#ples are shown in FIG 4.15 below.

(7attice arrange#ents in ionic co#pounds% #etals% and #olecular crystals are su##arised in chapter 5.) 4.66. >0ESTIONS 1) In chapter we i#plied that it was dangerous to tal" about causes% and about answers to the .uestion :whyH:. How do you e.uate this with sections 4. . . and 4. .2.H ) -hat #a"es heliu# unable to for# He #oleculesH 2) $ s#all highly charged positi!e ion is #ore li"ely than a big positi!e ion with a single charge to for# a strong ionic latticeH ;o##ent. 4) How can the forces which e(ist in an ionic lattice be responsible for the e(istence of ions within that latticeH $nswer the .uestion with reference to the for#ation of calciu# o(ide fro# i) calciu# ato#s and o(ygen ato#s ii) calciu# #etal and #olecular o(ygen gas. 5) -hy is the phrase :less screened fro#: placed in parentheses in this chapterH 5) >redict the si#plest for#ulae of all co#pounds for#ed between the following pairs of ele#ents% and predict the type of bonding found in each case: copper and Cinc% lead and o(ygen% potassiu# and bro#ine% chlorine and bro#ine% o(ygen and sulphur% sulphur and chlorine% berylliu# and chlorine% strontiu# and sulphur% hydrogen and sulphur% phosphorus and bro#ine% phosphorus and fluorine. In three cases% e(plain your reasoning. 8) >redict the shapes of '@ % ;@ % $l;l2% 3;l2% the I;u(H @)5J < ion% and ';l4. ?) 4raw si#ple bonding structures for 3@% 3@ % 3 @4% 3 @5% '@2 =% '@4 =% ' @2 =% '4@5 =% ' @? =% and ' @8 =.