Ue ce Sergey a / Gary Horner Brian Murphy David Tarcy mS OXFORDMeet the authors Sergey Bylikin was awarded a PhD in Chemistry from Moscow State University in 1998 and, one year later, received the State Prize of the Russian Federation in Chemistry. Until 2009, he was assistant professor at Russian State Medical University, after which point he tok up a role at the Open University in the UK. Sergey is an author of several textbooks. He has heen assaciated with the 1, since 2007 and was involved in the latest [& Chemistry curriculum review, Gary Horner, a graduate of the University of Queensland, las taught Chemistry since 1986 in Australia, Switzerland and Hong Kong. In his International School career Gary has held various leadership pasitions, including that of CAS caordinator and Head of Science, Since 2000, he has had significant involvement with the RO, attending warkshops acrass Europe and Canada and leading workshops in India, Hong Kong and Japan. In 20L0, he began advising on the IB Chemistry curriculurn review and isa member of the team developing the latest DP science course. Gary is eurrently teaching at King George V Sehool in Hong Kong. Brian Murphy graduated with a PhD in Inorganic Chemistry {rom University College Cork, Following postdoctoral and teaching posts in the UK and Ireland, he moved to the United Arab Emirates to take up a position a UAE Universit where he became Head of the Department of Chemistry and associate professar ‘of Inorganic Chemistry, Alter 8 years he maved back (o Ireland Lo lake up a post at Athlone Institute of Technology, where be is currently a senior lecturer, Brian has be sled with the IB sinee 1998 and was involved in the design of th latest 18 Chemistry curriculum, 2380 Dawid Tarey graduayed cus Jau.te with a degree in Setenge Education from, Whirworth College and has done graduate work sn sclences and information. technology In she Northwest USA and Queensland, Austral, He has taught In the USA, Australia, Europe, and Southeast Asia and bas been involved in ‘curriculum welling, moderation, and question setting for various exam boards and Institutions, David is active in many chemisuy education discussion boards, sam 1H Diploma Programme Chemistry Workshop J.eader and Fleld Representative and was Involved in the design of the latest IB Chemistry cursiculum. A project of this size would not have been possible without support and encouragement, Ta the greatest extent, the authors would like to thank their families for their love and patience, In particular, special appreciation oes to Brian Murphy - to my wife Mary, for all her love, understanding and unremitting support (mile buiochas!), parents, Teresa and Joe (RIP) who instilled in me an appreciation of internationalisatton from. an earl ;. Lorraine and her family: Gary Horner - to my parents Dennis and Myrtle tor thelr devotion, vislan and unwavering support of thelr children’s happiness, my sister Susan for ber evernal friendship, selflessness and professianal expertise; David Tarcy ~ to Tina Walton, my brothers Gary and Brian, for thei Input and suppomt, as well as the many friends and professional colleagues 1 have met through my waching career for their support, advice, and friendship; Sergey Byfikin - to Natasha for her patience, support and Invaluable comments,— ; ©) Worked example: explaining pH changes Construct a balanced equation. including state symbols, to explain hig pet cits apes fou the reacsion of matrogen ditceate with water Geceabiepe wy) Solution ‘© Nitrogen is a non-metal and therefore may form an acidic oxide. NO, reacts with water ta form a 1:1 mixture of nitfous acid, HNO, ‘and nltric acid, HINO, Nitrous acid Isa weak acid and nitric acid is ‘a strong acid. ©) We next write the balanced chemical equation: 2NO, + H,0 > HNO, + HNO, * Finally, we include the state symbok 2N0,g) + 1,04) ~ HNO, (aq) + HNO, (aa) © Because a mixture of acids is formed the pHt of the solution will be less than 7 (see tapte 8),QUESTIONS Questions What is the maximum number of electrons that can occupy ad sublevel? Ad B.S «6 D. 10 Which of the following elements can he classified as metallosds? Lal ML Si Ut. Te A Land itonly B and Ill only © Wand itt only D Ltand in How many valence electrons does selenium contain? Aa B. 6 G16 D. 34 Which of the follawing elements are alkaline ‘earth metals? L Rb Mi, st MI. Ba A. Land Il only B, Land Ul only C. Wand tt only D. 1, 1 and Which property generally decreases across periad 3? A. Atomic number B, Flectronegativity ©, Atomic radius D. First lonization energy 1B, May 2011 uw Which jon has the largest radius? A cl BLK: c. Br DF 1B, May 2010 What happens when sodium fs added to water? LA gas is evolved. 1. The temperature of the water increases, TL, A clear, colourless solution is formed. A. [and only B. Land Ul only C, Hand Ml only D. 1 Ih and It IB, November 2009 Which oxides produce an acidie solution when added to water? LPO» M. Mgo UL $0, A. Land I only B, Tand I only C, Wand I only D. 1,1, and 1H IB. May 2010 a1 Which statement about the elements in group 17 is correct? A. Br, will oxidize Cl BF, has the least tendency to-be reduced, C. Cl, will oxidize 1 D. 1, isa stronger oxidizing agent than F, 1B, May 2011 aal rend 10 How many of the folloning oxides are 12 Describe and explain what you will see if amphoteric? chlorine gas is bubbled through a solution of Na,0, MgO. AI,0,, S10, a), potassium iodide 2) Mane b) potassium fluoride. ul Ba 1B, May 2010 ee D4 15 ‘The alkali metals are found in group 1 of the periodictable of elements. 11 The periodic table shows the relationship a) State the full electron configuration between electron arrangement and the of K and its ion, K’ properties of elements and isa valuable tool far) yescrihe what you understand by the making predietions in chemistry. eet ena ey a} Identify the property used to arrange the ©) State and explain how the first innteation elements in the periodic table energies al the alkali metals vary going bb) Outline two reasons why down geoup 1 electronegativity increases across d) Explain yehy the tonic radius of K* is period 3 in the periodic table and smaller than the atomic radius of the one reason why noble gases are net parent atom, Ky assigued clectronegativity values, 11 e) Suggest why you should never taueh 1B, May 2010 an alkall metal with your fingers when working in ahe laboratoryIntroduction bonding — ionic, covalent, and metallic - and look covalent compounds, For covalent compounds shall see how a simple model, valence shell electron paie repulsion {VSEPR} theory, can be used-to determine the shape of a malecule, and we shall also look at some key chemical principles such as polarity and intermolecular forces. by metals losing valence electrons, > Negative ions [anions] form by non-metals er of electrons last or gained is, determined by the electron configuration of atom, The ionic band is due ta electro 0 atic attraction oppositely charged ions. betwe Inder normal conditions, ionic compounds are usually solids with lat Use theories to explain natural phenomena molten ionic compounds conduct electricity but lid ionic compounds da net. The solubility and © Applications and skills > Deduction of the formula and name of an ionic ‘compound from its component ions, including polyatamicions, > Explanation ofthe physical properties of ionic compounds (volatility, electrical eenductivity, and solubility) in terms oftheir structure melting p in observations, ofienic compounds can be used ===Aan ionic band refers tothe ‘electrostatic attraction ‘experienced between the ‘lectric charges of cation [positive ion) and ‘an anion {negative on). acne lonic bonding ons are formed when one or more electrons are transferred from one atom to another, The driving force for this electron transfer is usually the formation of 2 noble gas electron configuration, For example, the electron conliguration of sodium, Na is: [Ne] 3s! where [Ne] Is the noble gas core. & sodium atom can lose its ane valence (outer-shelly clectran to form the Na” cation, [Ne. That is: Na-@ = Na ‘We say that sodium is oxidized in this provess {it loses an electron) The electron configuration af chlorine, Chis: [Ne] 6°3p° Ifa chlorine atom gains an electran to form the Cl anion it will adapt a noble gas configuration, [Ne]3s*3p* or [Ar]. That is: clee = ‘We say that chlorine is reduced in this pracess (it gains an electron} Hence, the electron that is lost by sodium is gained by chlorine in the formation of the iwnic compound sodium chloride, NaCl Tonic compounds are generally formed between metals and non-metals. bbut note that the strict definition involves electrastatic attraction between a cation and an anion (for example, the compound ammonium chloride. NH,CL which consists of the ammonium cation, NH, and the chloride anion, Cr. is ianic, but does not contain a metaly. Let us take another example of an ionic compound, magnesium oxide. Magnesium is a group 2 alkaline carth metal, and so has two valence electrons: [Nep3s? “A magnesium atom can lose these two electrons forming Mg?*, which also adopts the [Ne] noble gas core. That ts Mg-2e > Mg Magnesium fs oxidized in this pracess, ‘Oxygen is in group 16, the chafcogen group. and so bas six valence electrons. The electron configuration af oxygen Is! (He]2s'2p* An oxygen aiom can gain iwe elecirons to form the O anion, which adopis a noble gas configuration: [Ne] or [tle}26%2p" That is: O42 +08 ‘Oxygen is reduced in this process.4A HONIG Henge, the two electrons that are lost by magnesium are gained by oxygen in the formation of the fonic compound magnesium onide, MgO, Under normal conditions, jonic compounds are typically solids, and have lattice-type scructures that consist of three-dimensional repeating units of positive and negative fons (figure 1) sedi ent horas ion ‘Figure Lace stueture of sium chlor, which cones of satin cations Na are hare anions [From the arc radi givin section 9 ofthe Got ballet you can seetha Ha (202 20°" m= 202 pr] is malas (181 10m 28 pen) [ee | a Table 1 Names of vanous ons The octet rule The octet rule has its own place in the discussion of chemical bonding and can be a useful starting point in trying to understand how chemical bonds are formed, The rule states that elements tend to lose electrons (hat is, undergo oxidation}, gain electrons (reduction), or share electrons in order to acquire a noble gas core electron contiguration, The first two processes are the basis of ionic bonding, The third process isthe basis of covalent bonding, which we shall discuss in sub-topic 4.2. a DING AND STRUCTURE "You should know the names ofthe various ans, their formulas and charges, including some xeanions oxygerscontaining anians, suchas NO, ,50,' etc) table 2), “© Ieisincorrecttause the term “malecule" when referring to jonic compounds: We newer ay “molecules of sodium chloride’, but instead “sodium chloride formula ‘units indicate that ions are involved inthe iatice structure. © General resin chemistry (such as the acter rule) often have exceptons, How many excoptons have to exist for arule twoceaseto beinguseful? + What evidence de scientistshave forthe existence ofions? What isthe difference between direct and indirect evidence? Topic 9 may holpyow when reflecting an this point. in which the oetetrule isnot obeyed?DIE © Worked example: deduction of the formula and name of anionic compound ‘Deduce the formula and name of the ionic compounds farmed between the following pairs of elements and/or polyatomic species: a) magnesium and fluorine d) calcium and nitrate ‘by aluminium and oxygen ‘e) ammonium and phosphate, -¢) sodium and oxygen Solution Combination Formula Name 3) | magnesium and fuasne Mes group 2,90 forma Mets magnesium fluoride Fisingroup 12,0 forms F; formula is MgF, b) | aluminium and oxygen Ais ingroup 3,s0 forms AP, aluminium oxide is in graup 16, so forms O° formula is A, «) sodium and oxygen Nais in group 1, se forms Na; ‘sodium oxide Osim group 16, so forms OF formulas Na,0 a) calcium and niteate {Cais ingroup 2,90 forms Cat"; calcium nitrate trates NO, | formula ts Ca(NO,), #) | ammonium and phosphate ammonium is NH," ‘ammonium phosphate Phosphate is PO? ; formulas (NH,),(PO,] {A Table 2 Formulas and names af seme inic compounds fram their cornpanentiong In namingioni binary compounds, AB, oneinting of amatsl and z non mots, te anding wil ide © Physical properties of compounds i ili Q, and inversely proportional ro the square Matin mad pone bats of the distance between them, 7. as given by onic campounds have high melting points i ainnaiV en oF ate and igh boiling points beeause of the strong ‘elecizosiati forces of attraction between the Fees ions in their lattice structures. For example, the e melting point of Natl is 801 °C and its boiling Hence, in the case af magnesium oxide, the two point is 1413 °C. In order to melt anionicsolid _—_clarges correspond to 2+ for the magneslum thee must be a large input of cnergy to break cation, Mg'*, and 2- for the oxide anion, O*. As apart the electrostatic forces. these Wo charges are greater than those of 1+ and 1~ in the ease of the Na* and Cl ions, the The electrostatic force of attraction, Fi directly 1 Shing point for MgO fs higher, that is 2852 "Cx ‘proportional to the interacting charges, Q, andVolatility Volatility refers to the tendency of a substance to vaporize. For joni compounds the electrostatic forces of attraction are strong, and so the volatility of such compounds is very low. Electrical conductivity For an fonic compound in the sold state the fons: occupy fixed positions in the lattice, Hence the tans are not free to move in the solid state, so solid jonic compounds do not conduct electricity. In contrast, in the molten state, the fons are free fo move and conduct elestricity, Solubility Ionic compounds dissolve in polar solvents such a5 water, bul do nat dissolve in non-polar solvents 4.2 Covalent bonding Understandings Acovalent bond is formed by the electrostatic attraction between a shared pair af electrons and the positively charged nuclei > Single, double, and triple covalent bonds involve one, two, and three shared pairs of electrons, respectively, > Bond length decteases and band strength increases as the number of shared electrans increases. Bond polarity results from the difference in electrone gativties oFthe bonded :toms. ed 4.2 COVALENT BONDING such as hexane, The molecule of water is polar and has partial charges itsell, om Hand © on ©, These partial charges are attracted to the ions in the lattice (lorexample, in the ease of sodium chloride, the #! on each H in the water molecule is attracted to the negatively charged chloride anion, Cl). As a result individual ions are pulled out-of the lattice and become surrounded by water molecules, In the case of a non-polar solvent, there is no attraction between the ions of the ionic compound and the solvent molecules, se the cations and anions remain within the lattice, Uses of ionic liquids Jonic liquids are efficient solvents and electrolytes, usedin electric power sources and green industrial processes © Applications and skills > Deduction of the potarnature of a covalent bond fram electronegativity values, @ Nature of science > Looking for trends and discrepancies — compounds that contain nan-metals have different properties from compounds that contain nan-metals and metals, > Use theories to explain natural phenomena ~ Lewis introduced a cass of compauinds which share electrons, Pauling used the idea of electronegativity ta explain unequal sharing of electrons. 97DIE Definition of a covalent bond ‘heovalent bond is formedby the electrostatic attraction betweema shared pairof electrons and the positively chargednuclel. According to IUPAC (the International Union oF Pure and Applied Chemistry].a covalentbond's a region of relatively high electron density between nuclei that arses atleast party from the sharingofelectrons and gives rise tan atwactve force and characteristic internuclear cistance, a Figure 1 Lewis symbols of three ‘laments, Nitrogen has five valence Sectrang, chlorine nas seven valence electrans, andancon has three valence electrons ‘Study tip Remember to deduce the number of valence electrons ofanelernent you can tise the group number forthe periodic table of elements. For example, sadiam (6:block] isin group 1, sohas one valence electron, calcium [also sblock) isin group 2, sohastwo valence electrons. Forthe pblock elements yau simply drop the ' in the group numberta find the number of valence electrons silicon (p-block) isin group 14, sohas fourvalence electrons. Fuuorine (also p-black) is in graup 17,50 hassevenvalence electrans, and so.0n. Covalent bonding In onic bonding we saw how atoms can either lose or gain electrans in ‘order to attain a nable gas electron configuration. A second type of chemical bond exists, however, in which atoms shace electrons with each ‘other in-arder ta attain a noble gas electron contiguration. This type of ponding is covatent bonding, and it usually uccurs between non-metal. In order ta look at this type af bonding im detall, fs useful first 60 introduce the idea of a Lewis symbol, which Is a slmple and convenient method ol representing the valenge {outer shell) electrons of an element, In sub-topie 4.3 we shall develop this further into what we term the Lewis (electron dot) structure of a compaund, based on a sysiem devised by the US chemist, Gilbert N. Lewis (1873-1946), Ina Lewis symbol representation, eack element is surrounded by a number of dots (or crosses). which represent the valence electrons of the element. Some examples are given in figure Let us consider the presence of covalent bonding in four different species, F,. O,..N,- and HE. Fluorine, F, Fluorine isin group 17, s0 Bas seven valence electrons. Hence by Acquiring one more electron, fluorine would attain 2 noble gas electeon configuration with a complete octet af electrons, The Lewis symbol for fluorine i E- + Ifo fluorine atoms share one electron each avith each other, cach fluorine atom gains one morc clectron to attain a complete octet of electrons, which results in the formation of a covalent bond between the two fluorine atoms, This covalent bond isa single bond and the shared pair can be represented by a inc: Foto Fs —ecFeF FF 4+ Note that in this Lewis structure of F, there are a total af six non- ‘bonding pairs of electrons (often called lone pairs) and one bonding pair of electrons Oxygen, 0, © Oxygen is in group 16, sw has six valence electrons. Hence by acquiring two more electrons, oxygen would attain a noble gas cleciron configuration with a complete octet af electrons + ILtwo oxygen atoms each share two electrons with eaeh other this ‘electron configuration an be achieved and results in the formation of a covalent hond between the Ove oxygen atams, This covalent bettd is a double band aid the two shared pairs can be represented by two Lines._— 4.2 COVALENT BONDING = © Note that in this Levis structure of ©, there are a tatal of four nen= bonding pairs af electrans ithe lone pairs) and twe bonding pairs of electrons, Nitrogen, N, Nitrogen is in group 15. 0 has five valence electrons, Hence by Acquiring three more electrons nitrogen woul! achieve a noble gas cleciron configuration with a complete octet of electrons {+ two nltrogen atoms each share thaee eleceronswith each other, this ‘electron configuration can be achieved and result n the formation uf a “covalent bons! between the two nitrogen atoms. This covalemt ond fsa {triple bond and the thee shared palts can be represented by three lines: NebeNe Se eNeo =Nr ‘© Mote that in this Levels structure of N, there are a total of ewe non- bonding pairs of eleetrans {the lone pairs) and three banding pairs of electrons. Hydrogen fluoride, HF © Fluorine is in group 17, so has seven valence electrons. Hence by acquiring one more electron, fluorine would attain a noble gas electron ‘configuration with a complete octet af electrons. Hydrogen is In group 1, so has just one valence electron. Hence by acquiring just one more electron, hydrogen would attain the noble gas configuration ef helium, + Note that hydrogen does not acquire an octet (the octet rule is historical in nature, and the key point to remember here for hydrogen isthe formation of a noble gas slectron configuration). # The Lewis symbols for hydrogen and fluorine are H* iF. For convenience we tse different symbols (a cross and a dat) for the clectrons in exch of the tivo Lewis symbols to signi different eleetrons for the two elements, + Twachieve noble gas configurations, fuovine and hydra ceach share one electron with each other, forming a covalent b This covalent bund is a single bond and the shared pair can be represented by a Line, H's Fie HEF H— Inthe Lewis stmucture of a molecule, the electrons Involved in the covalent bond ape indistinguishable, Activity Usings similar approach to ‘that of theexamples here, deduce the Lewis structures ofthemolecules earbon dioxide, CO,,and water, H,0, showing the steps involved in ‘the formation of the covalent bonds in each case,Introduction ‘There isa broad community of people working within a wide variety of scientific disciplines and approaching their inquiry with common methodology, terminology and reasoniny processes. Chemistry can be regarded as the central science, and mathematics the language of science. In this chapter we begin to lay down many of the foundations on which an understanding «1 chemistry is based, From the classification of maiter to the [UPAC © of the nomenclature of organic and inorganic compounds and the representations of chemical sanization reactions by equations, this chapter discusses the comprehensive language of chemistry For chemists, the mole concept ts of fundamental impartance, tts detinitions te relation (0 the number of particles, mass and! the volume of a gas elicit univ nderstanding and stuiehlametry, ahe quantitative method uf examining the relative amounts of reactants and products in a particular cher is developed. Treatment ul the applica intros cal reaction yas laws amd Ube of volumetric analysis complete Usis chapte Seen eer Chm Chey of matter and chemical change Understandings > Moms of different elements combine in fixed ratios to form compaunds, which have different properties from theircomponent elements Mixtures contain more than one elementand/ Ccreompoundthat are not chemically bonded together and so retain their individual properties. Mixtures are either homogeneous or heterogeneous. Nature of science ® Applications and skills 2 Deduction of chemical equations when reactants and products are specified > Application of the state symbols (s) (I), (g) ‘and [ag] in equations. Explanation of observable changes in physical properties and temperature during changes oF state Making quantitative measurements with replicates to ensure reliability definite and multiple proportions.DIE Analogy You can think of bond strength in terms of windows ~3 window thats tiple-glazedis ssronge than awindow that is louble-glazed, which incurs stwongerthan avindow with 3 single pane. bt 8 A Figure 2 Dipole moment representen by avectarin te poiarolecule, HF © Note that in this Lewis structure of HF there are a total of three non-bonding pairs of electrons (ihe lone paits) and one bonding pair of electrons Bond strength and bond length The examples above describe molecules with single, double, and triple covalent bonds. These bonds differ in bath bond strengtlt and bond length Bond strength The trend in bond strength is ‘That is, 9 triple bone is steonger than a double bund, whieh it turt is sltonger than a single band, The bond enthalpies in section 1 of the Beta dookler show this (table 1) Bond enthalptes will be discussed in subtopic 5.3 Bond length ‘This is the opposite trend to bond strength: pape ‘A single bond is longer than a double bond, which in cuen istonger than a triple bond, The covalent bond lengths in section 10 of the Data book itstrate this (able Pp. (ar 2551) lear | COvBEEN Bond length ‘pm 29 20 eta Ba 46 154 a Tabled Bond stenge ferthalpis) and ond lengths Comparison of covalent bonds and ionic bonds ‘We now understand the inherent differense between ionic and covalent bonds. Table 2 summarizes some of these differences Electronegativity ‘We saw in the case of bath fuorine, F,, and hydrogen fluoride, HE, that the single covatent bond is made up of a shared pair of electrons for each molecule, In the case of identical atoms, such as the two fluorine ‘tomes in F,, there isan equal sharing of the electrons in the shared pair hhetween the two atoms. This is nat the casc, however, im HF, and th shared pair is unequally shared between the hydrogen and fluorine atoms, In faet, you might think of this as a “tug-of-war” between the tho atomic partners for the shared pair! In reality, fluorine has 8 much_— 4.2 COVALENT BONDING lonic bonding Covalent banding. Formed between a cation (usually metal] and an anion (usually non-metal. Some cations (such as NH,*) canbe comprised of ‘nan-metals and some anians (such as Mad, } can contain metals, Usually formed between nar-metals, Formed fom atoms either losing clecrana [process of oxidation) cor gaining electrons (process of reduction] in orderta atzina noble gas electron configuration, Electorate atecton between oppositely charged ions, that is, a cation [positive ion) and an anian [negative ion} Formed trom atoms sharing clectvons with each ther in order to attain a able gas electron configuration. Electrostatic attraction between shared pairof electrons and the positively charged nuclal Ionic compounds have lattice structures. Covalent compounds cansist af molacules.* onic compounds have higher melting points and boiling points. Covalent compounds have lower melting points and boiling points. onic compounds havelow volatilities. Covalent compounds may be volatile lonie compounds tend to be soluble in water Covalent compounds typically ate insoluble in water. Ionic compounds conduct slecieity because ione-are fee to moveinthe molten state, They da noteonduet electricity when solid, however, 3¢ the ions are notfree to move Covalent cempoundsd net conduct aleesrcity beeause no ions.are presentts extry the charge. ‘4 Table2 ferences between ian and covalent banding "We shall d-scuss covalent network structures thal invalit latces late, greater attraction for the shared pair than hydrogen does and this leads tw what we describe asa polar covalent band, with one atom adapting ative charge, &, and one stam adapting a partial positive In this ease, since fluorine has a geeater pulling pawer far the shared pair of electrons in the covalent bond, it acquires the partial negative charge, #, and hydrogen then adopts the partial pasitive « This separation of charge can be represented vectorially by a a partial ney charge, 8 charge, dipole moment. symbol js {figure 21 Ifthe two atoms Involved in the formation of the covalent hond are to be a pure cavalent bond: that (s, the covalent band is non-polar and has ne dipole moment. Henee, the F Identical, the bond is s hond in F, isa non-polar covalent bond. ‘The US chemist Linus Pauling (1901-1994) introduced the idea of electronegativity (x,) as the relative attraction that an atom ef an element has for the shared pair of electrons in a covalent bond. Pauling devised a scale af electronegativity values, which can be found in section 8 of the Dada bookie. On the Pauling scale, fluorine iy the mast clectronegative element in the periodic table with a value of x, (sub-topie 3.2), There are certain trends in electronegativity values that mirror what we have already seen for the ionization energies across a period and down a group, ‘Tends in electrone gativitles “© Going from lett right across. period, x, values increas feosans: il decreasing atomic radi i) increasing nuckear charge. “© Goingdown a group. x, values decrease. fteosans: 40 iV increasing atomic radi i] primary screening [shielding] effect of inner elections,DIE ‘One of the main uses of electronegativity values is that we can Study tips ‘estimate, based on electronegativity value differences, x, whether 2 bond is ionie, pure covalent {non-polart, of polar covalent, This ne iceceneree ‘estimation is based on the rules in table 3 whicl you need to have an unsymmetrical dstibution of electron vemennber, density and are represerted by partial Bandtype ax, charges, 6 and 5 ‘© Forlonicbonds, we use full bd Ax> 48 charges to represent the pure covalent [nan-pelar] Ay=0 ions, eg + and —in thecase of Na. These charges are polar cavalent 0c Ay <18 not partial and hence we do not usethe 8sign, stable 3 ales to estimate whether bard is ni, pure covalent fren-pt ar aoar covalent For example, from table 3: F, xd F) = 4.0, Ay, = 0, s0 F hos a pure covalent (non-polar) Bond HF X,(F) = 4.0 and y,(H) = 2.2, hence Ay, = 1.8, so HF has a highly polar covalent bond NaF xy{F) = 40 and ,(Na) = 0.9, hence Ox, = 3.1, $0 NaF has ionie bonding, Chemistry In the kitchen Microwaves ae part ofthe electromagnetic spectrum (EMS), ‘as seen from section 3 ofthe Data booWet, The reason why microwaves ae so effcientatheating food relates tothe interaction of the microwave radiation of wavelength, A, (inthe range 1 rem to 1 m,conespandingta frequencies, vin the range 300GH2‘0 300 MHz] with the malecules of wate, H.0, presentin fad inthe liquid state Water consists of wa OH bonds, which are both pola, andvater selfs polae ‘molecule thi is explained later, Hence the oxygen side of the water molecule fs negatively charged and the hydrogen side ofthe molecule is positively charged, resuting in a net dipole moment: # ae * In foad. polar molecules of water absorb microwave 4 Figure 3 Imeraction of ler eharges sean on & sinusoidal radiation and constantly chenge their orientation [fip'), __#verepresentatoncf mcranawes [showing thir oiling aligning themselves with the alternating elactromagnetic 43} imtoracting with tho water maleculs present in field created by microwaves [figure 3). The fipping and food and eausingthem tofip ‘rotation of water molecules results inthe dissipation of ‘heat energy and increases the ternperature of the food.@ Worked examples: compounds Example 1 Deduice which of the following compounds are molecular: 2 50, * Pcl, + Ma,0 * NHNO, Solution 80, and PCI, are molecules as they contain only non-metals and no ions. In Na,0, Ay, = 2.5. $0 iis ionic fsinee 1.8}, Although it consists of all nen-metals, NH,NO, is, in fact, tonic becouse i consists of an ammonium sation, NH,*, and 4 nitrate oxoanion, NO, Remember that ionic compounds have lattice structures. Example 2 Deduce which of the bonds in the following binary compounds are ionic, pure covalent (non- polaz), of polar covalent: on, + Hel © KBr *co Buick question _— 4.2 COVALENT BONDING Solution In order to deduce this we need to-wotk aut Ax,. the electromegartvity difference for each bond in the varlous blnary compounds, and remember that Ax, = Os indicative of a pure covalent tnon-palar) bond, 0 < Ax, < 1.8 isindicative of ‘polar covalent bond, and Axx, > 1.8 fs indicative of an jonic bond. Ay, =0.508, polar) bond HC] x, (Cl) = 3.2 and x,{H1) = 2.2, henee Ay, = 1.0, so HCI has a polar covalent bond, with chlorine having a partial negative charge, f°, and hydrogen having a partial positive charge. 5°. i 6 a pure covalent (nom- Ker 3.0 and \,{k) = 0.8, hence 2.2, su KBr has tonic bonding with potassium having a 1+ charge and bromine having a 1- charge. 60 yX,(0) = 3.4 and y,(C) = 26, hence Ax, = 048, so CO has a polar covalent bond, With oxygen having a partial negative charge, and carbon having a partial positive charge, Expiain why, when you heat refrigerated bowl of soup in a microwave cooker, the saup clese tathe autside ofthe bow! can appear warm but nearthe centre of the bow! the soup can aften be coldya | GE LEO nner 104 4.3 Covalent structures Understandings > Lewis (electron dot) structures show allthe valence electrons in a covalently bonded species The “octet rule” refers tothe tendency of atoms to gain a valence shell witha total of eight electrons. ‘Some atoms, like Be and B, might form stable compounds with incomplete octets of elections. Resonance structures occur when there is more than ane possible pasition fora double bond in molecule Shapes ofspecies are determined by the repulsion of electron pairs according to the valence shell electron pair repulsion (VSEPR) theory. Carbon and silican form covalent network [giant covalent) structures. @ Nature of science ‘> Scientists use modelsas representations of the real world — the development of the model of molecular shape [VSEPR] to explain observable properties. @ Nature of science But a scholar must be content with the knowledge that what is false in what he says will soon be exposed ‘and, as for what is true, he eam count on ultimately seeing it accepted, if only he lives long enough Ronald Coase (Recipient. of the Node! Prize in Economie Ssienees ie 1991), Ronald Coase (1910-2013) was the oldest living. ‘Nobel laureate until his death an 2 September 2013, © Applications and skills > Deduction of Lewis [etectron dot) structure of molecules and ions showing all valence electrons Forup to four electron pairs on each atom, ‘The use of VSEPR theory to predict the electron domain geometry and the molecular geometry far species with two, three, and four electron domains. Prediction of bond angles fram molecular geometry and presence af non-bonding pairs of electrons. Prediction of molecular polarity from bond polarity and molecular geometry, eae (eaeneeaeeet ete ce ater ae include but are not limited to C,H,,€0* and 0. Explanation of the properties of covalent network [giant covalent] compounds in-terms oftheir structures. Scientists use madels as representations of the real ‘world = for example, ¥SEPR theary as a model ‘of molecular shape has been used 10 explain ‘observable properties. Every model In sclenice Is built on certain assumptions = one of the major considerations for a sclentist is to appreciate the validity of a madel, its limitations, and whether it will withstand the test of time. VSEPR theory: isane such model, although not without its imitations.4.3 COVALENT STRUCTURES Lewis (electron dot) structures Earlier in this tapic we introduced the idea of a Lewis symbal, which shows the number of valence electrons of an element represented hy either dats or crosses, From this we developed the idea of Lewis (electron dot) structures, based an the formation Gof the covalent bond sn a molecule, In a Lewis structure, each pair of electrons can be represented in a number of diiferent ways = either by two dats, by two etosses (ur a combination of a dat and a cross), or by a lime. For example, some of the ways in which the Lewis structure of phosphine, PH,, might be represented are shown In figure 1a). ‘A Figure d (a) Two dots, two crosses (os combinaton ofthe twa), oraling can be usedta reprasant each pairof elections ina Lewis [olectran den} suctue,[b] Lewis (election ot] structure of CC Remember the band angles shown in 3 Lewis structure do nat necessarily represent tho actualbond angles in the molecular geometry In such a representation it Is important to distingulsh between: © bonding pairs of electrons (showing the covalent bond as single, double, or triple bonds) and + non-bending paits of electrons, often called the lone pairs, Which ate pais of electtons not invelved i the bonding, In the Lewis structure of phosphine there are three bonding pairs of electrons and ane tone pair. Similarly, the Lewis structures of cazban dioxide, CO, and carbon monoxide, CO, which contain multiple bonds, can be represented as shown in figure 2 reset ‘A Figure 2 Lewis In CO, each double bond represems two bonding electron pairs, amd Ln CO, the triple bond represents three bonding electron pairs Lewis structures help us understand the different types of covalent bond {single, dauble, or triple bonds} and the existence of lone palrs in molecules. However, Lewis structures tell us nothing about the actual shapes of molecules, and hence the representation of the Lewis structure of a molecule may be drawn with a geometricalDIE The chemical formals of ammonium nitrate is often veritten aS NH,NO. but in reality it is made up of cation, ammonium, and an oxoanion, nitrate. When yaw write Lewis: ‘Structures af cations or anions, including axoanions, you ‘should always include square brackets ond the charge in the representation. arrangement that differs completely from its real shape in space. For example, the Lewis structure of carbon tetrachloride, CCl, is typically represemted as in figure Ib, which might suggest the ‘exiitence of 90° €1-C-Cl bond angles, In fast the shape of the carbon Ictrachloride molecule is tetraltedral with 109,5° C-G-€l bond angles, We shall shorily see how to deduce this shape based oma ‘very uselul model far predicting molecular geametries, called the valence shell electron pair repulsion (VSEPR) theory, Lewis [electron dot] structures of cations and anions and ionic compounds Lewis structures can be written not oily for neutral molecules but also fot cations attd antons, In a compound containing both a cation and af anion there iS an eleeteostatic attraction between the oppusitely charged ions, which fortis the ionic band, However, the bonding ‘within the cation and ation separately may be eavalent in tatare: far ‘example, in atimaniuin nitrate, NINO, (figure 3abh the bonditig in INHL[* ahd in [NO,) is envalent, even though the bonding between the Catia and the aihion is tonic, In the ease af ainimonium chloride, NIL,Cl (figure 34h)) the Lewis structure of the chloride anion ean be represented with the chlorine surrounded by eight dots te reprevent the eight valence electrons present in the anicn, by 4 et -evalensbonds| nthe sation alos bonds ‘nthe anion lore bonds between tho estan ant the alon —sashocampound wees ee lonicondsbetween the exten antthe anion sothe compound aveall ionic Figure (4) Lasse strurture of arnenanium nites, (b) Lewis steueture of ammeniins bride Valence shell electron pair repulsion (VSEPR) ‘theory Much of the core understanding of chemistry involves discussions ‘of structure and bonding. Every molecule has a particular shape and as chemists we need to have the ability ta always think in three dimensions_— 4,3 COVALENT STRUCTURES : a, 4 cy Op 0, oat Hr os _aFigiret(3] 20 representation athe drugtramadol whose leer forma CH Tramadel is 3 etal sesingsymhetc oped analgesic use din vesting Severe pin (0) Thee.cimensiaral moleeua' space. fag model of tama. The atoms are represented spheres and.are colar coded:caruen [prey], hgiragen (white, itvogen [ve], and waygan red) No, As mentioned previausly. Lewis structures are two-dimensional representations and ultimately tell us nothing about shape. Valence shell electron pair repulsion (VSEPR) theory can be used to deduce the shapes af covalent molecules The basis of this theory is ay follaws since electrons are negatively charged subatomic particles, pairs of elecizans repel one amotlter ta be as far apart as possi in space In order 10 determine the maximum angle that can be achieved from, thls electron pair-electron palt repulsion (ry tying a number of balloons logether. Then examine the spatial shape the balloons ultimately adopt. In the case of twa balloons a linear geometry is obtained, with the 1wo balloons aligning at 180° to each other. Think of dividing a circle up inwe haves: 42 = 180" (figure 5) ‘s Figure 5 Twe balloons tec together showings linea arrangementin space In the case af three balloons, a trigonal planar arrangement i generated. similar to taking a circle and slicing it into three segments: 22 — 120" Hence the balloons arrange themselves to lie on one plane al 120° ir each other (the term planar in chemistry means flat (figure 6), Now consider tying four balloons together. Thinking Ln twe dimensions, you might visualize taking a circle and dividing 360° by 4, which would give a bond angle berween any 1Wwe of the balloons of 90°. This Is not What happens: in thrree-dimenstonal space the balloons maximize thelt spatial arrangement tw-be 109.5° apart — try #! This shape creates a tetrahedral geometry (figure 7) You might imagine the tetrahedron sitting in the environment of a cube lo help you appreciate the three-dimensionality of this geometry based on the repulsion of four electron pairs (figure 8)GE LEO nner “a Figure? Four balla tied Vopether hawing atetiahedralartangement a Figure @Atetrahedranfiesntoa cube space athreedimens A Figure 6 Thine tatlaons ted together showing 1 trigonal planar arrangement n space The hasie molecular geometries can therefore he summarized, as shown in table the basis of two, three, or four pairs of electrons, Each pair ‘af electrons is described as occupying an electron demain, which you might like to imagine ax being a field of electron density Tad. 1707 au; 16 & | Wumberof | Woleculargeometry | Bondangle | Examples of 7 electron molecules or ions éa hhaving this sh two 3 180 ” BeC!,.C0, ae three 120 BF, [NO] ‘4 Figuie 9 The Scottish scientist, engineer, and inventor, Mexander raharn Bell 1847-1522 T siting in his tetrahedral chair Most Famous tevaheatl fornis invention ofthe telephone, Gel was alco fscinatedby the thacry of engineering a structures and ight. He championed the four 1095 cause of tetrahedral structures, irmeworks OH, INH} [00,] based ana series ofinterlocked tetrahedra, He s seen nere watching Wiss of his hte designs 4 Table 1 Molecular geoenetries based an two, tee, and faut electron domains The set of three molecular geometries, AB, (linear), AB, (trigonal planar), and AB, (tetrahedral), © adi also be extended 1o generate al shapes for species that have fewer bonding pairs of electrans than the number of electron domains present. In such cases, the electron_— 4.3 COVALENT STRUCTURES domains not accupied by the bonding pairs of electrons are filled by non-bonding pairs of electrons (lene pairs). In such eases, three additional molecular geometries are generated: ABE (V-shaped or bent), ABLE {trigonal pyramidal), anid AB,E, (V-shaped or bent), where E represents a lone pair of electrons {table 2). We can therefare distinguish berween: © the electran domain geometry (based an the toral number of ‘electron domains predicted from VSEPR theory}; and + the molecular geometry (which gives the shape af the molecule}, To Illustrate this Idea let us take the example of the water molecule 1,0. The number-af electron domains predicted {rom VSEPR theory Is four (we shall learn how to deduce this shortly). This means thar the electran domain geomeny Is tetrahedral. However, from the chemical formula we see that there are anly two OH bonds, which suggests the presence of nwo handing pairs (not four). The other n aceupled by two Jone pairs of eleetrons. This implies that the actual molecular geometry, based on an AB,E, structure, is V-shaped or bent (iatie 2), Number of | Electron | Molecular | Band angle | Examples of electron | domain | geometry molocules orians domsins | geometry having this shape F ‘tigoral planar | ¥shaped je ree ABE {bers} | 120 See INO] Retumingto the balloon anslogy, 4yousan see this inaction if au , | tetrahedral | agonal | 5 again take four balloons andsie fe ABE pyramidal 109.5° | NH, [80,]°, [,0] ‘them together Thistime have ‘wa ofthe balloons blue and towahedrat | V-shaped 5 ‘wa ofthe balloons yellow the four ABE, {bent} | $1085 Ho.[Na,] latter epresertinglone pairs of electrons. Make the two yellaw | ible 2 Geomewies moving ane pais based on twse ond faut electron domains balloons biggerthan the two bie ballons [the textopposite Bond angles in molecular geometries: explains why). To emphasize the eee ois See A vr factthatthelane pairs are nore Lone pairs nf eleattons affeet the bond angles ina malecule, Bere pairs Pinipis geceevoe escupy mere space than bending pairs, so they decrease the band angle os eae ieeaee benween bonding paits, The degree uf electron pair-elexteon palt eek omer balee Tel repulsion follows this ender: NSE oe aries LPILP > LPIBP > BPBP ‘the electron domain geometry isdesignated ae evahecral, but where LP represents lone pairs of electrons and BP represents bonding | jure madeuper eae boning pairs of eleetrons. ieeer pa acta Table 3 illustrates how repulsion between lone pairs of electrons bonding eleevon pais, Aeereases the bond anglesMinne a oid) @ The atomic theory ‘A universally accepted axiom af science ‘today is that all matter is camposed of atoms, ‘However, this has not always been so, During the seventeenth century the pitlogistort tkcory ‘wasa widely held belief, To explain the process col combustion it was proposed that a fire-like clement called phtogiston, said to be found ‘thin substances, was released during burning. ations of burning metals revealed that magnesium in fact gains rather than loses mass when it burns in oxygen. contradicting. the phlogiston theory. Sclentisis use a wide range of methodologies, Instruments, and advanced compuatng power ‘wo obiain evidence through abservarion and ‘experimentation. Much of the technology commonly used today was mot available to scientists in the past, who oftem made ground- breaking discoveries in relatively primi conditions to {ced their appetite for knowledge. ‘Over time, theories and hypotheses have been. tested with renewed precision and understanding. Some theories do not stand the test of time. The best theories are those that are simple and accaunt for all the faets, ‘The atomie theory states that all matter is composed af atoms, These atoms cannot be created or destroyed, and are rearranged during ‘chemical reactions. Phy teat and chemical properties of matter depend on the bonding and arrangement of these atoms. Anoine Lavoisier (1743-1794) States of matter efi tefered mn asthe ‘Tathet of Matter is everywhere. We are made up of mattes, we consume it, it modem chemisiny. His conmibialon surrounds us, and we can sec and touch many Jorms of malier, Ait isa to seience is well dacumented. In form af matter which we know is there, though we cannot sce it. Bur 1772 Lavoisier deoveredttvough planet and the entire universe arc made up of matice and chemistry experimentation thatwhen sulfur secks to expand our understanding of matter and its propertics. and phosphorus were combusted they gained mass, These results contradicted the belief that mass would be lost during combustion a3 phlogiston was released, Could pnlogiston havea negative ‘mass? Empirical data derived ‘ors Lavolsier’s experiments was eventually accepted by the scientific: community. Kis work contained sSonie ofthe frst examples of ‘quantitative chemistry and the Jaw of conservation of mass. His ‘experiments may appear simple by present-day standards but they were ground-breaking intheleday, The discovery of angen by Joseph Priestly and Catt Schecte invalidated the phiogiston theory. Thisisan ‘example ofa paradigm shift. The dominant paradigm orbeliefis replaced by a new paradigms this how scientific knowledge progresses? 1 4a Figure 1 The characteristics of mamerDIE Molecule Numberof | Molecular geometry | Bond angle electron domains " an ch, four \. 109 5° i, ain wey NH, four 8 102" geal ME Ko four 104.5" 4s Table 3 Effect of lone pairs on bond angles @ Interpreting the VSEPR model Using the model of YSEPR theory it is not possible to predict exact bond angles when lane pairs are ‘present, All-you can state is that the bond angle will be expected to be less than predicted from the hond angle associated with the basie shape However, LP|BP and LP(LP repulsions shauld he taken into account. A common mistake that many students make is to learn the experimentally determined bond angles for ammonia (107°) and ‘water (104.5°) and then assume that all trigonal pyramidal molecular geometries and all V-shaped molecular geometries also have these bond angles, This is a mistaken interpretation of the VSEPR. model. For example, phosphine, PE, also has an AB,E structure anid is trigonal pyramidal, but its H-P-H bond arigle drops to 93.5%, Likewise, hydrogen sulfide, #,5, is ¥-shaped, based on an AB,E, structure, but the H-S-H bond angle is much lower at 92.1°, The bond angles are affected by many factors, so making exact predictions is not feasible. Two other factors that play a role are electronegativity differences and multiple bonds {the latter also occupy more space, just like lone pairs). For example, in the molecule of ethene, the H-C-H bond angle is 117°and the H- ‘C=C bond angle is 121°, even though both would be predicted to be 120° based on a trigonal planar arrangement about each carbon: © Working method to deduce both Lewis (electron dot) structures and electron domain and molecular geometries ‘We can combine Lewis structures and VSEPR theory in a simple-to-use working method. The following method can he used to deduce Lewis structures and electron domain and molecular geometries: 1 Draw a ball-and-stick diagram, identifying the central atom. Bach stick represents a pair of electrons in the covalent bond, Don’t worry about hond angles at this stage - you can draw the sticks in any direction ta commencethe process. In the case of oxeanions, localize the negative charges on any terminal oxygen atoms: the remaining bunds should be eonverted into double bonds. In the case of other anions (not oxoaniens) and cations ‘use square brackets and place the charge outside these, 2 For the central atom, deduce from its group. number in the petlodi¢ table the number of valence electrons. 3 From the number of sticks, count the number of single bonds, which we shall designate as sigma (7) bonds. 4 Add one electron for each negative charge (bur nos for localized charges airendy assigned to oxygen atoms in oxoanions in step f). Delete one electron for a positive charge. Subtract one for each pi (x) bond. 5 Combining steps 2, 3 and 4, divide this nomber bby two fo obtain the puraber of electron pales, which equals the number af electron domains. 6 Based on the number of electron domains, deduce the electron domain geometry. 7 Determine the number of lone pairs present if applicable, and deduce the molecular geometry. Then draw an exact representation of the structure. complete with predicted bond angles, taking into account the order of, electron-pair repulsion LelLP > LFiBP > BeiBP 8 Finally, draw a Lewis representation by completing the octets eit all terminal atom exchiding hydrogen (which will already have attained a nable gas clectran configuration of two), Remember to ineude square brackets for any cation of anion, 9 Draw any resonance structures (explained an poge 115) where applicable. et us put this working method to the test, There are three types of structure that yau are required to work out © Basic shapes — AB, {linear}, AB, (trigonal planar), and AB, {tetrahedral}, # species with lone paits of electrons - ABE (V-shaped), AB,E {trigonal pyramidal), and _— 4,3 COVALENT STRUCTURES ABE, (¥-shaped) ~ all with associated bond- angle considerations © Oxoanions. Worked examples Example 1: Carbon tetrachloride, CCI, A balleandestick diagram for CCl - a * Chas four valence electrons (it is in group 14): four 2 bonds; so the ta J number of valence electrons is elght; so there are four eleeiron domains. Thus the eletrom domain geomeary is temahedral (a2) ‘© There are four C-Cl bonds 30 no lone pairs are present — the molecular geamciry és therefore tetrahedral and tee bond angle will be 109.5° a vas tel 0 a \ a ¢ Finally you need te complete the octets an each terminal C1 in order to generate the Lewis structure. Example 2: Ammanium cation, [NH,]* ‘© Ball-and-stick diagram for [NH.]*:Gn eee) tia se has five valence electrons fas itis im group 15) four ¢ bonds; one positive charge: s0 total number of valence electrons = 8; $= 450 4 electron domains Electron domain eomeny is teteaedrat (AB) © There are four N-H honds sa no lone pai are present ~the moleular geometry 1 therefore Jetrahedral and the bond angle will be 109.5", © The above structure is also a valid Lewis structure as hydrogen is surrounded by two electrons, which is the maximum number of electrons permisellle Example 3: Nitrogen trifluoride, NF. + Ball-and-stick diagram for NF, ste F ‘© WC has five valence electrons {as itis in group 15) three ¢ bonds; so the total number of valence electrons is eight; £24, s0 there are four electron domain $4.0 th four electron d Bletrom domain geometry is tetrahedral (AB 2) ‘© There must he one lane pair present, as there are only three N-F covalent bonds. Hence the -malecutar geomecry is trigonal pyramidal and the band angle will be lose thant 109.5" due to the presence of the lone pair (which occupies mare space} — the repulsion between LP|BP is greater than that between BP|BP. ale a NSE ‘The experimentally determined F N F bond angle, which cannot be determined precisely from ‘the model, is 102.2", suggesting that not only is the lone pair influencing the bond angle but also the difference in electronegativity is lekely to play arole. * Finally, you need to complete the octets on each terminal F in order to generate the Lewis srustare eae <208, = Example 4: Sulfur difluoride, SF, O- * 3 has six valence electrons (group 16); two a bonds; so the total number of valence electrons is eight $= 4, s0 four electron domains, Electra domain geometry is tetrahedral (AB,E,) © There must be two lone pairs present, as there are only two $-F covalent bonds. Hence the molecutar seomeary is V-shaped and the bond angle will be fess than 109.5% due to the ‘presence af the two lone pairs, which occupy much more space. The repulsion between a LPILP is greater than that between a LP|BP which is greater than that between 2 BPIBR, so the hond angle is reduced significansiy {rom its predicted value of 109.5%, s Fama ‘The experimentally determined F § F bond angle, which cannot be determined precisely from the model, is 98°, showing the significant sole of the LP|LP repulsion in operation (also- the electronegativity of fluorine will have an influence}. © Finally you need to complete the octets on. each terminal F in order to generate the Lewis structure:Example 5: Nitrite oxoanion, [NO,] © This is an oxoanion, so in the ball-and-stick diagram we first localize the ane negative charge on any one af the two oxygen atoms. Since oxygen hava valency of two, this means the other nitrogen-to-oxygen bond must be a double bond. Note that in the ease of an oxoanion, we first begin with square brackets with the negative charge outside, but we then localize the charge ‘on any one of the wo oxygen atomsand remove the square brackets unill later ip our stepwwise working method, © N has five valence electrons (as it is in group 15): two. bonds; ‘one pl tn} bond, which counts as —14it is Important to remember this: see the bax below’: ‘the total number of valence electruns is six; 6 $= 3 so there are three electron domains, Hlectron demain geometry i arigonat planar (AB) How to handle zr bonds in VSEPR theory -r bonding involves off-axis bonding. 28 we will explain in topic 14. Hence, as the shape of a molecule is controled by the bonding framework along the interniclear axis, in counting the valence electrons we subtract 1 foreach = bond present. For SL students, _you donot need to go inta the reason behind this (the “explanation is given at HL but you do need to know the method invoived. ‘You cantthink of itike this—the shape is controled by the geometrical anangementalong the interwuclearaxis, where the. bonding framework lies. Adauble bandis described as.a7 +x] bond anda triple band is described as ao +2] band, To reduce these back to bonds, you simply subtract ut the s components ed 4.3 COVALENT STRUCTURES ‘Oxesnions Inthe case of oxoanions, we do not addan additional ‘electron here forthe negative charge an the nitrite ‘oxoanian because this hos already been secounted for in the frststep, Thisi¢a very important point ans you needto note this difference forexoanions, Tree eee ee Bie reine ee aed T Gpatl dese ee eaeaie peace shaped ond the Borel engl lle lar than Tar ue ia the perien ef eet kare le Gilaraee peal nue gee : “es The experimentally determined bond angle, which cannot be determined precisely from the model, is 115°, © Finally you need to complete the actets on each terminal © in-arder to generate the Lewis structure: - AN ier Nate that for the oxygen containing the double bond. completing the octet entails the addition of two lone pairs, whereas for the oxygen with the single bond im this structure, completion al the octet requires the addition of three kane pairs. The actual structure of nitrite isa combination of two contributing Lewis structures, This is resonance, which we shall return to shortly. Contributing resonance structures are represented by a dauble-headed Ge oe RS oes ae ‘The two nitrogen-to-oxygen bond lengths in te are equivalent and intermediate in length between a single and a double bond. The two contributing resonance structures therefore could be combined, cach represented with square brackets and the negative charge placed outside,DIE Example 6: Sulfite oxcanian, [SO,]° This isalso an oxoanion, se in the ball-and- stick diagram wre first localize the two negative charges on two of the three oxygen atoms. Since oxygen has a valency of two, this means the other sulfur-to-oxygen bond must be a double bond in onder to satisfy this valency for oxygen. ‘© 5 has six valence clectrons {as itis in group 14): three 7 bonds; one wband (1); so the total number of valence electrons is cight: 4 = 4, so there are four electron domains, Electron domain geometry is tetrahedral (48,2) ‘* There must be one lone pair present, as there are only three sulfureto-oxygen covalent er bonds. Hence the molecziar geometry is trigonal pyramidal and the bond angle will be less than 109.5" because of the presence of the one lone pair, which occupies much more space. 5 i So = as ‘The experimentally determined bond angle, which cannot be determined precisely from the mode 106". Finally you need to complete the wetets on ‘each terminal O in onder te generate the Lewis structure a Note that for the oxygen containing the double bond, completing the octet involves the addition of two lone pairs, whereas for the two terminal oxygen atoms with the single bunds in this structure, completion. of the octet requires the addition of three fone pairs. The actual structure of sulfite is a ‘combination of three contributing resonance structures; ‘The three sullur-to-oxygen bond lengths in sulfite are equivalent and intermediate in Iength between a single and a double bond. Inmost Lewis structures, the central ator will be utrounded by an octet ofelectrans, However, in some ‘species, the central atom will have less than an octet of valence electrons; these are incomplete octets {for ‘example, the linear molecule beryllium chiovide, BeCl., which has the central benylium atom surounded by ‘only four electrons, or the trigonal planar molecule boron trichloride, BCI, in which the central boron atom is surrounded by only six alectwons): Inather spacies, an expanded octet is possible This is discussed in topic 24. In such cases altemative Lewis, sthictuies involving octets may be used,_— 4.2 COVALENT STRUCTURES Resonance structures ‘As we sau in the case of the nitrite oxeanion, sometimes it ix possible for Lewis structures to have identical arrangements af atoms but different arrangements of the electrons, The Individual Lewis steuctures that contribute to the overall structure are called resonance forms, The actual electronic structure of the species is called a resonance hybrid of these resonance forms. In order te represent this idea of resonance, the contributing resonance forms are linked via a double-headed areow. One of the best known examples of resonance is the molecule benzene, C,H, igure 10) C -O bl Oo ‘a Figure 10 [a] fea Kekule structures of benzene showing resanance (b] Representation of benzene showing the deloraized nature of ts x electrons: The two resonance forms represented here are termed the Kekule structures of benzene, In benzene, as can be seen fram section 10 of the Data dorkle, each carbon-to-garbon bond length is 149 pm, intermediate between a carbon-to-carbon double bond (134 pm) and a carbon-to-sarbon single bond (154 pm). The structure of benzene, therefore, is often drawn as in Figure 10(b), where the circle represents the delocalization (which wre shall discuss further in topic 10} In topic 14 we shall discuss resonance in mare derail, together with = electrans and bond arder. Molecular polarity Earlier it this topic we diseussed the idea of bond polarity. We now focus on molecular polarity, that is, whether the molecule itself Is polar of non-polae (figure 11). The polarity of molecules is distinct from the polarity of individual bonds; @ non-polar melecute may have polar bonds, In order to deduce the molecular polarity we can follow a simple three-step working method described in the box below. Working method te deduce molecular polarity 4 Using VSEPR theory, deduce the molecular geometry. 2. foreach bond present, using electronegativity differences, hy. deduce the ‘bond palarity foreach bond present and draw the associated dipole maments; these are best represented as vectors Using vector addition, sum all the dipole moments presentto establish ‘whetherthere is anet dipale moment, j,forthe molecule, I 50, the molecule is polar Resonance involves using wa or more Lewis structures to represent ‘particular molecule arion. A resonance structure is ene of two or more alternative Lewis structures for amolecule orion that cannot bbe described fully ith one Lewis structure alone, Indetocatization electrons are shared by more than two-atomsin a molecule or jonas opposedto being localized between a pairof atoms, on por ete ule Ho Sul polar molecule wl H por motocate ‘a Figure 1 Examples ofronspalar and polar ralecules. The net cigole-mament, af polar melecule can be reproserted vactorilly The dipole moment represents the non= symmetrical stitution of eharge in polar ralecule [compared witha syrnpateca ciseiburtion of ehargeina nor polar ralecule], Inthe vecter the head of the wector represents & andthe teil rapresenté 5GEOL ean © Worked example: deducing molecul: Deduce the molecular polarities of the following: a) SP, b) co, Solution a) SF, As seen in an earlier worked example ‘on VSEPR theory, the molecular geometry ‘of SB, fs V-shaped. From section 8 of the ata bookier: (8) = 246 and y,(F) = 4.0 Hence, fluorine Is more electronegative than sulfur and the § F bond is polar with the following dipole moment: Ss $F re & Ta deduce the molecular polarity, we need to sum the two S-F vectors. The SF, smalecule is ¥-shaped 30 we add the two vectors using the parallelogram law (bee Study tip below): Study tip In deducing molecular polarities based on molecular ‘geometries you need ta find the vector sum ofthe Individual dipole maments, The parallelagrarn law is & useful method. V,.and both vectars start from the Same paint, the the vector sum). ‘The parallelogram lw. f you have two vectors Vand Sutn ofthe twa weetors, ¥, can be found by completing ‘the parallelogram. The diagonal wil give the resultant » polarity V+ 2, = 7. This resulis im a net dipole moment, 4; the molecute is polar. <1085" co, Using VSEPR theory, carbon dinxide is found to be a linear molecule, From section 8 af the Pata booklet XplC) = 2.6 and x(0) = 3.4 ence, each C-O bond (Ay, — 0.8) is polar, The two vectors are equal in magnitude but ‘opposite in direction and hence cancel each ether out, resulting in no net dipole moment, that is, = 0, The molecule is non-polar (even, though it has two polar bonds), Atug-ofawraris a model that can be used to consider vectors on the same line (axis) “A Figure 12 Students in Mantserrat in anug.of-wat, Both teams ‘are pulling slang the same as More polarbonds (resuiting from agrearerliference: electronegatvity, &.x,] win the tugsofwas, pravided the pullis along the same axis4.2 COVALENT STRUCTURES GY. Allotropes Allotropes of the same element can vary in both physical and chemical | Definition of allotropes properties, As described by IUPAC, allotropes are diferent structural modifications of the same element. Cathan Is.one of the most fascinating elements in the periodic table forms on Earth are based an earban. Carbon has a number of allowopes: graphite, diamond, graphene, and C,, fullerene Covalent network solids © Graphite, diamond, and graphene are examples of covalent network solids. cavalent network solid is one in which the atoms are held together by covalent bands in a dimensional lattice structure gin large networks or chains}. Another well known example of a covalent network solid is quartz, which is silican dioxide, $10, © In contrast, C,, fullerene is molecular. Graphite Graphite is an example of a covalent network solid. In graphite there are layers of hexagonal rings consisting of carbon atoms. These layers are connected by weak intermolecilar forces of attraction, which are called London (orces, leading to the use of graphite 2s & lubricant and in penils (the so-called ‘Iead”in our pencils is not lead but carbon in the form of graphite), Each carbon atom adopis a trigonal planar ecomeity, and is covalently bonded to three other each carbon atoms ata bond angle of 120°. The coordination ausabet of each carbon epermes ot taveeen is thees in the structure. Although the covalent bonds are strong network solids writhin the sheets, the London forces betwecn the layers are weak “+ Motng points. Covalent which allows the layers to slide past each other, and thas graphite network olds have igh can be used s a lubricant (figure 131, Unlike other covalent network meting points (upicaly solids, graphite i a good conductor of electricity as it has delocalized gfesterthan 1000°Cang + electrons mich igherthan the meting points of molecular substances) + Alectical conductivity. Covalentnetwor solids ae poor electrical conductors fanjaawea! graphene are leer exceptions ~ electrical conductivny i one ofthe characteristics that makes graphene remarkable). «Solbity They ate ypcaly ingolubl in carnmon saber + Horahess, Generally. covalent network: sols ar hard, 4 Figure 13 Graphite covalent network soll that consists of exogoal lagers of carbon though in graphite the ayers sea hen pect pr ec ek a canskde pastone ante. farce of traction [Landon forces|AFFigure 14 Disrnond gan alletrope af carbon vith acovalent network atice strurture, Large crystals of diamond are mined foc use as gemstones, Small crysta's are used as on industrial abrasive, High-quality crystal of ‘damand are foundin Seuth Africa, Russia, Brazil and Stera Leone International perspective Throughoutistony diamands have often been a potential ‘saurce of significant global conflict The term "blood diamond? hasbeen cained tadescribe diamondsmined inregions of canflict and subsequently sold to fund such conflicts. What responsibilities donations and governments have in the import of praducts suchas gemstones and precious ‘metals? Useful resource Look at the history of the discovery of graphene and current research developments inusing this material atthe University of Manchester, UK, the university where Geim and Nowoselov did their research 10 vin the Nobel prize in Physics in 2010, hupswwwgrephene. manchesterac.ukistory/ GEOL ean Diamond Diamond is also a covalent network solid. In the lattice structure of diamond, each carbon atom is covalently bonded to four other carbon atoms in a tetrahedeal arrangement, with a €-¢-C bond angle af 109.5 (figure 14). The coordination number of each carbon within diamond is four, Diamond is one of the hardest substances known because of this nily bonded interlocking structural arrangement of tetrahedra. For this reason diamond is offen used in heavy-duty cutting teols such as ‘saws, polishing tools, and dental diitts. ‘The melting and boiling points of diamond are very high (3550 and 4827 °C, respectively), Unlike geaphite, im diamond the valence electrons are localized isi the single o covalent bonds, and therefore cannot move Ircely. This means diamond does not conduct electtisily. Strong covalent bonds in diamond make it is Lnsoluble in all common salvents, @ Diamonds are forever? thas been said that “diamonds are a girl's best friend”, but have you ever considered if diamonds last forever? Unfortunately not! Under ambient conditions, diamand is thermodynamicatly unstable and eventually turns inter another alletrope cof carbon, graphite, However, at room temperature this process Is extremely slow, se diamond is sale to be Riveticatly stable, At 100°C the conversion of diamond ino graphite accelerates and at 1700°C in completes within seconds. When we talk about stability in chemistry we need to consider both dhermodyiansic stability and Aires stably. Graphene — the super material! Graphene is not only one of the thinnest and strongest ofknown materials, but it is also the first two-dimensional crystal ever discovered. Graphene is a covalent network solid, but differs from graphite in that it consists of a single planar sheer of carbon atoms arranged hexagonally (figure 15), and is only one atom in thickness. As in graphite, each ‘carbon atom is covalently bonded to thrce other carbon atoi coordination number of cach carbon in graphene is three. The carbon sso the atoms are densely packed in a honeycomb erystalline lattice, but the lattice is actually planar, which makes it remarkable as a erystalline structure ‘The experimental evidence for the existence of graphene was obtained in 2004 by the Russian sclemtists Andre Geim and Konstantin Navoselov, who won the Nobel Prize in Physics in 2010 for their ground-breaking ‘experiments at the University of Manchester im the UK, Graphene is an excellent thermal and electrical conductor, 300 times mare e(fictent than capper. A piece of graphite 1 mam thick consists of three million sheets of graphene, with ane stacked an top of another. When graphite Is prised apart it becomes essentially graphene. Ifaf= 4.3 COVALENT STRUCTURES graphene sheet is rolled up, it forms. ¢arbon nanotube (sub-topic A.6) When this, in turn. is folded up into a sphere it becomes a fullerene, whicl looks like a seccer ball (discussed belorr) Graphene |s a remarkable material, especially because of its superb electrical conductivity, strength, flexibility. and transparency. Graphene has been described as the “new silicon”. Some of the future applications of graphene lie in the following research areas + development of graphene-plastic composite materials to replace metals used in the aerospace industry because of their ky density and high strength © liquid-crystal displays (LED) and flexible tmuch-sereens for mobile devices due 1 the flexibility, transparency. and electrical conductivity al graphene After the discovery of graphene in 2004 a whole class al two-dimensional materials have emerged, which include the single layers of boron nitride, BN and molybdenum disutfide, MoS,. BN is an excellent lubricant and can be usedl in a vacuum so itis important in space research and is also used in ceramic materials, MoS, is also a very good lubricant C,, fullerene In 1985 2 new form af carbon allotrope called fullerene, with carbon atoms arranged im closed shells, was discovered by Robert F. Curl Jr (working at Rice University in the USA), Sir Harold W. Koto (working aL Suscex University in the UK}, and Richard E. Smalley false working at Rice University). In 1996 these scientists were awarded the Nobel Prize in Chemistry for their discovery of fullerenes. The number of carbon atoms in the shell was found to vary. which led to the discovery ‘af several new carbon structures. Fullerenes were found te form when vaporized carbon condensed in an atmosphere of an inert gas. Clusters of G,, and C,, were initially synthesized, with more C,, than C,, clusters being formed, The structure of each C,, molecule was found to consist of a truncated icosahedral cage, whieh has the shape ofa soccer ball. The spherically symmetrical C,, molecule was unique in nature at its time of discovery, In the C,, polyhedron cage there are 20 hexagonal surfaces and 12 pentagonal surfaces, and each carhom atom fs covalently bonded to three others so that the coordination number fs three. but the arrangement is not planar (figure 16) The geodesic dome designed by the US architect R. Buckminster Fulley for the 1967 Mantreal Warld Exbibitien in Canada has this shape of a soecer ball and hence €,, has been named buckminsterfullerene. These spherical fullerenes are sometimes referred to as buckyballs Gyo fullerene is nat a covalent network solid, and so is different from. graphite, diamond, and graphene. C,, is compased of individual molecules with strong covalent bonds, but with weak London forces henween the molecules, A Figure 15 Graphene Graphene nanoribbons- the ‘tute landmark in the fk traphene! Find our about grophene nanarisbens (GNRS} by accessing the chemicat Inerature or online and why are material seientists so excited about thelr future development, ‘a Figuie 18 Molecular structure oF, fullerene [buckminsterfullerene} showing GO earn ators arranged ln aspherical structure vat consists cfinterlinking hexagonal are pentaganal rings, ea soccer ball= Ke The properties of the three states of matter are summarized below, Solid fixed volume © fixed vorume fixed shape © no fixed shape = takes the shape = . ‘of the container it accuples cannot be compressed cannot he compressed . © forces between particles are weaker than in solids attractive forces between particles hold the particies in a dlose-packed arrangement © particles vibrate. rotate, and + particles vibrate in fixed translate (move around) positions The way the particles of matter move depends on the temperature. As the temperature increases the average kinetfc energy of the particles increases ~ the particles in a solid vibrate more, The particles in liquids and gases also vibrate, rotate, and translate more, Temperature There are a number of different temperature scales. The most commonly used are the Fahrenheit, Celsius, and Kelvin scales All chree are named in honour of the scientist who developed them The SI umic for temperature is the Kelvin (Ky. The Kelvin seale is used! in ‘energeties calculations {see tople 5)- Absolute zero is zero on the Kelvin seale, 0 K (on the Celsius scale this is -273 °C). Iis the temperature at which all movement of particles stops, At temperatures greater than absolute zero, all particles vibra even ip solid matter. You can convert temperatures from the Celsius scale to the the Kelvin scale using the algorithm: ‘temperature (Ky = temperature (°C) + 273.15 Changes of state If You heat a block of ice in a heaker it will melt x0 form liquid water. 1 you cominue heating the water, twill boil 1 form water vapour. Figure 2 shows a heating curve for water ~ it shows how ils temperature changes during these changes of state, We shall look at the relationship between Temperature and the kinetic energy af particles during these changes of state. oa @ no fixed volume no fixed shape = expands to occupy the space available can be compressed forces between particles are taken as zero particles vibrate, rotate, and translate faster than in a liquid 51 [Systeme international) units are 2 Set of standard units that are used in science throughoutthe world. This will be discussedin great detail in sub-cpic 1.2. ‘When describing eam termperaure, we might say’25 degrees Celsius [25 °C}'or 238 kelvin (298 K)'(t the nearest kelvin). Note thatwe use just the wort kelvin, not degrees kevin. he bling point of water is 100°C or 373 K, and the motting point of -watoris O°C 0 273K. evaporation /=t03m sernpornure wnat ‘a Fiquo2 ehoatingeurwoforwatcrFigure 1? Seucturewfquarta which crystalline frm of sil diane, $0, Crystals of quartz are usedin optical and Selemtfic instruments and in eleetanies, such va quartz watches GEOL ean Fullerenes are black solids that do not dissolve in water, but can dissolve in sume non-polar solvents (for example, benzene). In organic solvents they form coloured solutions; the colour depends on the solvent and varies from red to brown to magenta. €,y, unlike both graphite and graphene, does not conduct electricity. Although il does contain delocalized electrons, the electrons do not have the capacity to move from sane 6,, molecule to the next heeause of the symmetrical nature of C,. Many new compounds of fullerenes have heen synthesized subse quently ‘with atoms or small molecules enclosed within che fullerene eage. Such Inclusion complexes can potentially be used as gene and drug carriers: ‘other applications be Ln the areas af superconductivity and ferromagnettcm because of the unuswal electromagnetic properties of inclusion complexes. Fullerenes also have the ability to fit Inside the hydrophobic cavity thar forms the active site of che human immunadeficeney virus (£1¥} protease ‘enaymes and hereby inbiblt them Carbon nanotubes are tube-shaped molecules, closely related to C.,, and have electrical conductivity approximately ten times better than ‘copper and are 100 times stronger than steel, They are alsw used in many electronic applications, replacing silicon, and in the synthests of new compounds that allow unsiable substances to becume stabilized when incorporated within the iubes. The diameter of such tubes is ‘exiremely small, in the order of 107 mm, en the nano seale, Buckyballs and carbon nanotubes have became a vibrant and dynamic area of ‘chemical research in materials science, with numerous applications. @ Serendipitous discoveries The accidental discovery of buckminsterfullerene [sa classic example of the importance of serendépity In chemistry. Carry out same research: In the library and online to find out how buckminsterfullerene was discovered. What other examples af serendipitous discoveries are famous in chemistry? Silicon dioxide, Si0, (quartz) Silicon dioxide, $i0,, often called silica, is found in ity amorphous form (that fs, a solid with no ordered structure) as sand, In ils mest common crystalline form 11 is ealled quartz, Quartz is another example of a Unree-ditensional covalent merrork solid. Tt consists of arrays of SiO, lettahedra arranged in a lattiee éligure 17), Eack silicon atom is bonded covalently to four oxygen atoms and cach oxygen atom fs bonded ‘covalently to Wo silicon atoms, The Si-O-Si geomertical arrangement is bent because wf the presence o two non-bonding pairs of electrons ‘on each oxygen atom, Silicon dioxide has both a bigh melting peitt (1710°C} and a high boiling poist (2230 °C) due to the existence of strong covalent bonds, both erysialline and amorphous dioxide ave insoluble in water and solid ‘crystalline $10, does not conduct electricity (since there are no delocalized electrons present) or heat. Note that m electricity however as electrons a -n silican dioxide can conduct ¢ [ree ta mave in the moken state_— 4.2 COVALENT STRUCTURES ‘The term coordination bond Is often used (based on Coordinate covalent bonding We have just considered covalent network solids. Apother 1 handling is called coordinate covalent bonding, In 2 typical band, the shared pair of electrons originate from both atoms tha formn the bond; one atom contributes ane electon to the shared pat and the second atin contributes the second electron. tn coordinate covalent bunding. the shared pair of electrons comes irom only one of the two atoms; this atom donates both electrons to the shared pal A number of species have coordinate covalent bonding. Examples include: + Nn] © 9} + co © alcl, © transition metal complexes (discussed in tople 13), Ammonium cation, [NH,]* when ammoni NH, reacts with an acid, H!, the fone pair on the nitragen in NH, combines with the proton, EC’, 1o form the ammanium cation, [NE] HN: +H 5 NEL Hydronium cation, [H,0]* aa a cme Carbon monoxide, CO <#o: Dimer of aluminium chloride, Al, Cl, TUPAC recommendations] ‘to designate coardinate covalent bond. ‘The coordinate cavalent bond is representedby on ariow ‘to signify the origin of the electrons in the bond, Once formed, however, all the bonds are equivatent (whether coordinate covalent er narmal covalent). Previously, the ‘term dative covalent bonding was used forthis type of band but, based on IUPAC recommendations, this term is naw largely obsolete,ya | GE LEO nner Inthe sold state aluminium chloride is fonie, AICI, is six-coordinave involving an omic latte (lust with sigmiffcant eavalent characteristics). At atmospheric ‘pressure it sublimes at 180 °C, On insreosing the pressure it mells, On melting ‘at 192.4°C il forms the dimer, Al,CL,, which has coordination bonding, In this structure, aluminium is telrayalent witha coordination mumber of four, The three-dimensional structure of the dimers shawn in figure 18, The bridging -chlarinesare on a different plane compared ta the terminal chlorines. us stare up to 400 °C, Above nal ¢ AL,C], molecules predominate in the gas this temperature, It dissociates tw form molecules of AICH, with a trig 44 Figure £8 The structure ofthel,0, cimerin the gaseous phase planar geometry (120° bond angles) Representations of structures Fortetrhedral structures itis cammmon to use wedge and-dash notation ta shaw the various planes: ‘© a wedge indicates thatthe bond i in front the defining plane ‘© adach indicates that tha bond is behind the definingplane Quick questions 1 Apart tom atu oid, ently tren other substances mat sublime real Deduce whetherboth solid and mltn alutiniu ‘hlvide conducts electricity. ‘© 2 cold ine indicates that the bondlies on the defining piane. For example, the tetrahedral structure of methane, CH, can berepresented as follows using this notation: 4 | won cf 4.4 Intermolecular forces Understandings ‘> Intermolecular forces include London (cispersion] forces, dipole-dipole forces, and hydrogen bonding. > The relative strengths of these interactions are London [dispersion] forces < dipole-dipole forces < hydrogen bonds. © Applications and skills > Deduction of the types of intermolecular force present in substances, based on their structure and chemical formula. Explanation of the physical properties of covalent compounds (volatility, electrical conductivity, and solubility) in terms.of their structure and intermolecular forces. @ Nature of science Obtain evidence far scientific theories by making and testing predictions based on them — Londen (dispersion) forces and hydrogen bonding can be used to explain special interactions. Far example, molecular covalent compounds can existin the liquid and solid states. Ta explain this, there must be attractive forces between their particles that are significantly greater than those thatcould be atuibured to gravity, 122@ Theories on intermolecul: In sub-topics 4.2 and 4.3 we saw that there are intramolecular forces of attraction that hold the atoms together within a molecule, resulting in covalent bonding. Such intramatecular forces affect molecular geometries, physical properties, and reactivities of compounds. Intramolecular forces could be described as “bonding * forces of attraction. Another type of attraction, intermolecular forces, are interactions between malecules within a compound (figure 1}. Intermolecular forces are largely responsible for the Bulk properties of matter, thar is, its physical properties such ae ‘melting point and boiling potn i a F: Hviie Ht covalent bond intermolecular force of attraction ‘a Figure 1 Diference between intramolecular and intermolecular forces wf stration forhudrogen Putri, Tis intamolecur forces result in cavalent berting Intermolecular forces of attraction are much weaker than evvalent bonds. For example. the standard enthalpy change of vaporization of water. AF. (the enthalpy change associated with the conversion af one mole af pure liquid into a gas at its boiting point at standard pressure, 100 kPa) is 44.02 Ki mol (at 298 Kk) whereas 926 kI mol is required to break the two O-H polareovalent bonds in a molecule of water (see the bond enthalpies for 0-H from section 11 of the Datta hooklet:2 x 463 = 926 ki mol"). Since the intermolectlar furces of attraction are relatively weak, the molecules of a cavalent compound are not held strongly together and. for this reason, many cavalent compounds are gases (for example, N,{g), 0,(8), CO,{2) and CO(g)) oF liquids (for example, 1,041). In cuntrastfonic compounds have very strong electrostatic forces of attraction between the ions, meaning that ionic compounds are solids at room temperature and have high mehing points, For example, the mehing point ofthe cd 4.4 INTERMOLECULAR FORGES forces ionic compound sodium chloride. NoCl(s} 33 801 °C, ‘whereas the melting point of water. H,0(3), which is acavalent compounds, is much lewer, at 0 °C: Chemistry in the kitchen The nexttime you are having a drink with cubes af ice Init, take one cube of ice and try ta break it with your fingers. As you will discover ths is virtually impossible ‘and the reason for this can be associated with the Intermolecular farces of ataction in the vast network of water molecules presentinthe ice. One of the assumptions made in topic 6 in relation to-the kinetic-molecular theory of gases is that collisions between one gaseous particle and another are completely elastic, This suggests that gascous atoms or molecules do not stick or adhere to one another. This is incorreet because every gaseous species can be converied into a liquid at some temperature. It is the existence of intermolecular farces of attraction that enable molecules of a covalent compound to exist in the condensed phase (liquid and solid). Figure 2 demonstrates an example of this. As Seen intopic the particlesin a slid orliquid ate Aightly packed togethor— that is why we use the term condensed pha ‘a Figure 2 Spem bank shipping contines being filed with liquidntvagen to keep the sper zen, We think af warogen Asbaingin the gas phase, but al gases can be converted into quis a same temperature because of the ners ecular forces. atacton between the molecules he bling poi of lquidnitrogen is ~195.8°Cat atmospheric pressureDIE In order 10 understand these bulk physical on the theories, London (dispersion) forces. and properties, we need to widen our discussion hydrogen bonding, two types of intermoleeular and take inte account intermalecular forces of forees of attraction can be used to-explain special attraction in all three phases, solid, liquid, and gas. interactions. For example, how molecular covalent ‘The question, therefore, is what are the various compounds cam exist in the liquid and solid states. types of intermolecular forces of attraction that _As stated above, the explanation is related to scan be present? In selence we obtain evidence for selenitfic theories by making and testing predictions based: The relative suengths ofthese ieractionsin general are: Landon forces < dipole-dipole forces << hydrogen bonds However, we shall also consider ‘exarnples where London forces are stronger than dipole-dipole forces, buttheabave orderis, what accurs often! the existence of attractive forces between their particles that are significantly greater than those that could be attributed to gravity, The main three types of intermolecular forces of attraction that we shall discuss are: © London forees {also called dispersion forees oF Instantanenus Induced dipole-induced dipole forces) + dipole-dipole forees © hydrogen banding. Culleetively the frst wo intermolecular forces (as well as dipole. induced dipole forces) are termed vam der Waals forces, as specified by TUPAC. person) forces + dipale- Inpentane, there lorge contact sen aera the entive maeenle for In 2,2metnyiprspane thre much smaller contact ae fr odjacem molecules interact. adjacent molecules tnirteract. | Figure B Spacestling madelsof pentane and 2,2sdimethylorapane showing areas af meen adjacent molecules fr Leon forces of attractionAs the contact area is musts larger between molecules of pentane, ahe London forces between the molecules will have 2 greater magnitude, which results in a higher boiling point for pentane, Dipole-dipole forces ‘The second type of intermolecular forces are dipole—dipale forces, which exist in all polar molecules with a permanent (not instantaneous) dipole moment, ., Examples of such molecules include HE, ICI. HCL, and CH,CHO. In this type of intermolecular force, there is an attraction ‘between the positive end of onc permanent dipole and the negative end of another permanent dipole on an adjacent molecule. Let us compare the boiling paints of two molecules that have similar ‘malar masses: the interhalogen. iodine monochloride, ICl. and the halogen, bromine, Br, (table 4). or ‘Types of intermolecular —_ i Since ICLis highly polar, in addition to London forces it also has dipole dipole forces of altraction between the ICI molecules (figure 6), which Jead toa higher boiling point. a Tabi Baling points of Cl and,_— 4.4 INTERMOLECULAR FORGES a tipele-spele force f amaetion| ‘A Figure? Dipsle—dipale force of atraction between permanent poles on adjacent meses 2) Note that iedine asa larger atomic radius emmparedte ehlatine [ses section ef the ‘Dato boaklet) but chieene ls mare lectronegative [see section cf the Data Booklet Hydrogen bonding This third type of intermolecular force holds a special place in chemistry and is une of the most important types of intermolecular foree, Hydrogen bonding can accur between molecules when there Isa HF, an O HL or an N H band present. A cypical hydrogen bond may be depicted as: X=He Y=2 | rytgen band where the: © hydrogen donor is XH © accepyor may be an atom oF an anion, ¥, a fragment ar a molecule ¥-Z in which ¥ is bonded 10 Z * hydrogen bond is represented by the three dots though dashes are sometimes used. Hydrogen bonds oceur, for example, henween ay water molecules, H,0 Bb) ammonia motecules, NK, ¢) hydrogen luoride molecules. HE 4) water molecules and dimethyl ether molecules, (CH,),0 a} ee ‘ vw Hydrogen bonding alten has a large influence on both the praperties and structures of materials. Definition of the hydrogen bond ‘As recommended by IUPAC in2011,3 hydrogen bond is defined asan attractive interaction between a hydrogen atom froma molecule ora molecuiar fragment, X=H.in which Xis ‘more electronegative than H,andan atom ora group ofatomsin the same ora different molecule, in which ‘thoreis evidence of bond formation. ‘Pure.ond Applied Chemistry, 183(8), [2011] pp1637-1641 Key point The HF, O- Hand NH bonds ‘are polar covalent bonds and ‘are not hydrogen bonds Representation of hydrogen bonds In this book we use dashes ‘0 epresenthydrogen bands to distinguish them from lone pairs of electons.A Explain why the temperature ofa boling, liquid does notincrease despite energy being constantly applied, 2 Deduee which would be ‘more painful, seaiding your skin with water vapour at baiting water. 9 Explain why you might (eel «old and shiverwhen you get autafthewateratthe beach ‘oma very hot, windy day. Freeresdrying isa food preservation technique: ‘that uses the process of ‘sublimation, Facds that require ‘dehydration ae frst frozen and then subjected areduced pressure, The frozen water ‘then sublimes direety to water vapour, eFeetvely dehydrating ‘the food, The process has. widespread applications in areas autsidethe foodindustyy ‘such os phaimaceuicals {vaccines}, document recovery for water damaged baoks, and ‘clentficreseareh laboratories, ‘Figure’ Changes af tate Fer water Minne © What happens to the particles during changes of state? © Asa sample of ice at—10 °C (263 K) is heated. the water molecules in the solid lattice begin to vibrate more. The temperature increases: until it reaches the melting point of water at 0 °C (273 K). © The lee beging to mele and a solid-liquid equilibrium is set up. Figure 2 shows that there is no-change in temperature while meliing is ogeurring. All of the energy Is being used to disrupt the lattice, breaking the attractive forces between the molecules and allowing the molecules to move more Ireely: The level of disorder Increases. (The navure of the forces between molecules is discussed in sub-topie 4.4.) © Once all the ice has melicd, further heating makes the water molecules vibrate more and move faster, The temperatuce rises until it reaches the boiling point of water at 100°C (373 K}, and the water staris to boil. © AL 100°C a liquid-gas equilibrium is established as the water I ‘Again the temperature does nat change as energy is required 10 overcome the attractive forces between the malecules in the liquid water in order ta free water molecules from the liquid 10 form a gas, (Equilibrium is covered in sub-topic 7.1.) © The curve in figure 2 shows that while the water is boiling its temperature remains at 100 °C, Once all the liquid water has been converted 10 steam, the temperature will inerease alrove 100 °C, © Mching and boiling are endothermic processes. Energy must be transferred to the water from the surroundings to bring about these changes of statc. The potential energy (stored energy) of the molecules increases ~ they vibrate more and move aster. © Cooling brings about the reverse processes to heating - the condensation of water vapour to form liquid water, and the freezing of liquid water to form a solid. * Condensation and freering are exothermic processes, Energy is transferred to the surroundings from the water during these changes of state, The potential energy of the molecules deereaves = they vibrate less and move slavrer, © Vaporization is the change of state from liquld to gas which may happen during boiling. or by evaperation at temperatures below the boiling point. In sublimation matter changes state directly from the solid ta gas phase without becoming a liquid. Deposition is the reverse pracess of sublimation — changing directly from a gas to a solid. Elements and compounds ‘An element contains atoms of only one type. Atoms of elements cambine naa fixed ratiato form compounds composed of molceules or ions. These rearrangements of the particles of matter are the fundamental cornerstone ‘af chemistry, represented in formulae and balanced chemical equations. (Uxcoms are covered in detail in sub-topic 2.1.)