CHAPTER 2: ATOMIC STRUCTURE (more detail) Models Atomic spectra Orbitals The electrostatic approach Predicting electron arrangement

Electron arrangement and the periodic table More information from the periodic table Predicting properties 2.1. INTRODUCTION 2.1.1. On e t!e n"m#er o$ ne"tron%& 'roton%& and ele tron% in an atom has been deduced, it is possible to construct models which represent the arrangement of these $"ndamental 'arti le%. At elementary le els of chemistry a simple model of the atom is used in which the neutrons and protons are placed in a nucleus at the centre of the atom. The electrons are considered as occurring in spherical shells around the nucleus. They are held in position by the electrostatic attraction between the positi ely charged nucleus and the negati ely charged electrons. The relati e si!es of the nucleus and the electron shells are well illustrated by imagining a hydrogen nucleus the si!e of a pea on the centre spot of a large football stadium. The electron shell would only "ust be contained within the stadium. 2.1.2. U%e$"lne%% o$ t!e model: #hen considering much of an atom$s beha iour, this model is still useful at this le el. %t should not be considered as incorrect any more than &%'. 2.1. should be considered an incorrect model of an aircraft wing.

and in order to (eep scientific method more generally in perspecti e.. using the clarified understanding we gain from a model.......2. detailed.. and rationalise obser ations. %n other words. for e)ample.more detailed properties. . but the latter model ser es a different purpose.. An important role of theory is to unify +sections 1. the shell model may be more helpful when trying..or ... E en fewer are theologians9 %n these two respects... and may be too comple) for simple aerodynamics. the model describes the beha iour in terms of5 . models help us to ma(e predictions. at higher le els of chemistry we encounter models of the atom which probably loo( more li(e the real thing +section 2... we are merely describing the beha iour by saying that the attraction is consistent with pre ious obser ations on particles which we ha e classified as oppositely charged. and rationalise0 them. collate.-.... science has probably suffered as it has become more established. to predict the effect of atomic si!e on the ease with which outer electrons are lost. . for e)ample.. and the e)tent to which they merely help us 0describe.. .owe er.. we may ha e a model of electrostatic attraction which has positi e charge attracting negati e charge. %t does not loo( as much li(e an aircraft wing as the rele ant part of a polystyrene construction (it.i.1.. aphabetical letters are the most useful models of atoms.. more fundamental. At another le el.. *imilarly. #e only 0e)plain0 beha iour when. for e)ample. %t is also important to understand the balance between the e)tent to which models help us 0e)plain0 obser ations.. At one le el we can e)plain the attraction of protons for electrons by saying that they are oppositely charged.1. or general than the obser ed property of attraction +study /uestion 1-7 8uestions li(e this are absolutely essential in order to (eep theory rele ant to obser ation and e)periment.. %n such cases we can cautiously use words li(e 0because0 and tal( about cause and effect. the description of the beha iour may be greater than actual e)planation.2. we may be able to describe beha iour in ad ance....1. when writing e/uations..1. by helping us describe... The (ey /uestion is this5 6oes the concept of charge describe a property which is. &ew scientists are philosophers.or iii.. E en then...... Also.ii.This model of a wing is useful when illustrating simple aerodynamic principles..-. and 14...... collate...... &or e)ample.. Moreo er.more fundamental properties...more general properties... 3. .

%n response to these data. This produces an absorption spectrum. #hen the radiation is analysed in more detail it is seen to be emitted only at certain precise fre/uencies. T!e %!ell model is a response to information from atomic spectroscopy.corresponding to mo ements of electrons between precise energy le els around the nucleus +pictured as spherical shells in the shell model-. but only at the same precise fre/uencies as those obser ed in emission spectra. atoms of an element can absorb electromagnetic radiation.1.2.2. *imilarly. so:called.2. E. ATOMIC SPECTRA 2.hf.f λ. it has been proposed that the radiation has precise energy alues +related to fre/uency5 . The radiation is obser ed as a. . %f an electric current is passed through an element in gaseous form at low pressure. electromagnetic radiation is emitted. emission spectrum.

they emit electromagnetic radiation. when electromagnetic radiation is passed through the gas. by an electric current.g.and on returning from higher to lower le els.%t is proposed that emission spectra occur when electrons are e)cited into higher energy le els +e. This . it is suggested that electrons are e)cited to higher energy le els by absorbing radiation with e)actly the energy difference between the two le els. <on ersely. The energy of the radiation emitted is e/ual to the energy difference between le els.

orbitals are best imagined as regions of electron density.2. in the isible region. . =y contrast.produces an absorption spectrum because on returning to lower le els. the characteristic rainbow series of colours is produced. &or e)ample.(. d.. s. Each has a characteristic shape shown in &%'.. dar( lines of 0missing light0 would be seen. the spectrum is continuous li(e sunlight.. 2.. #hen sunlight is split by a prism. Each orbital can hold a ma)imum of two electrons. %n pictorial terms. the electrons release energy as heat. 2. 2..ed atomi %'e tra show that the proposed energy le els are more finely di ided than described by the shell model.. %n the case of an absorption spectrum. and f.1. light produced by an emission spectrum and split by a prism would be obser ed as bright lines of particular colours. an orbital is the geometric space around the nucleus in which an electron with a particular energy is most li(ely to be found. More $inel+ re%ol. when light is produced by heating a solid or li/uid. OR)ITA*S 2. T!ere are $o"r t+'e% o$ or#ital. =oth these processes produce line spectra. A model consistent with this e)tra information has the electron shells +energy le elsdi ided into sub:le els (nown as orbitals. p. =earing in mind the dual particle>wa e nature of electrons.

2. rather than tal(ing about their energy. the types decrease in energy in the order f ? d ? p ? s. . there are se en f:orbitals per energy le el.. from the second le el onwards. from the fourth le el onwards. Ele tro%tati a''roa !5 %t would be far too great a brea( with tradition to tal( solely about electrostatic attraction of the nucleus for the electrons in orbitals.owe er.. Then. &inally. there are fi e d:orbitals per energy le el. there are three p:orbitals per energy le el.There is one s:orbital per energy le el. energy is an essential concept if we are to de elop our models of atoms. &rom the third le el onward. the orbitals of a particular type are initially e/ui alent in energy... %n a gi en energy le el. . Moreo er.

.1. *ee also section 11. .owe er. THE E*ECTRON ARRAN.... ii. this is shown as 2p1.enient to represent orbitals by bo)es. PREDICTIN.2.. an electron with a low energy is attracted strongly by the nucleus. 2.. and if there are two electrons in one orbital. 2p15 2p1.The electrons are found in the lowest energy orbitals a ailable +Aufbau principle-.g. %n the shell model such an electron is far from the nucleus and easily remo ed +a low amount of energy is needed to remo e it-... %n the shell model it is close to the nucleus and difficult to remo e +a high amount of energy is needed to remo e it-. E. T!ree r"le%5 There are three important rules which describe the way in which electrons are distributed amongst the orbitals of a particular atom5 i.. we are tal(ing about an electron which is not attracted ery strongly by the nucleus.EMENT 2. In %ome a%e% it i% more on..1.Each orbital can hold a ma)imum of two electrons.. %n the bo) notation electrons are shown as arrows..1. <on ersely. %f there are four electrons in the 2p orbitals. rather than drawing out their shapes5 An e en simpler notation shows the number of electrons in a particular set of orbitals by using an indice. they are shown to ha e opposite spins. it is important to remember that when we tal( about an electron with a high energy.-. 2. .1. E.g. and these ha e opposite spins +a ersion of Pauli$s e)clusion principle-.. The arrow head represents a spin direction.

Ele tron arran/ement and t!e 'eriodi ta#le5 The energy ran(ing of the orbitals is deduced by starting at the top left hand corner of the table and tra elling across the periods. <learly it is necessary to (now the energy ran(ing of the different types of orbital in order to apply these rules. the easier you will find large sections of physical and inorganic chemistry. d:orbitals. one at a time +i.g.1. because the more familiar you are with the periodic table.2. but it is far more appropriate to wor( it out from the layout of the periodic table.iii. the three 2p orbitals. This is particularly true. do not fill until the s: orbital in the ne)t energy le el is filled.und$s rule-.are occupied singly before pairing occurs +.e. This is why the energy le el of the d: . which occur from the third energy le el onwards. There is a gimmic(y diagram which allows you to wor( out this ran(ing. wor(ing through the elements in order of the number of electrons they ha e. 2.Orbitals of e/ui alent energy +e. from left to right. as wor(ed out from atomic number-.

s2 .d2 1s2 @i 1s2 2s2 2p3 .d14 1s2 1p2 2 .orbitals is always one behind the period number.p3 . Electron configurations of some elements.s2 . %t is somewhat confusing that orbitals in a generally higher energy le el.2. suggesting they ha e a higher energy than the 1s orbital.d1 1s2 D 1s2 2s2 2p3 .3. &or comparable reasons.2 The period number is e/ual to the number of the highest energy le el +outer shell.d orbitals are empty.d. 1s2 <r 1s2 2s2 2p3 . 21 22 2E 2B . calcium.s2 . @ote the apparent idiosyncrasies at chromium and copper5 1 . .p3 . A simple consideration of potassium. 1s1 .d orbital. 2 12 1B 21 2.p3 .el%5 The highest energy electrons in potassium and calcium are found in the 1s orbital rather than in a . &%'.s2 .p3 1s1 *c 1s2 2s2 2p3 .dB 1s2 <u 1s2 2s2 2p3 .p3 .e 1s2 Ai 1s2 2s1 = 1s2 2s2 2p1 P 1s2 2s2 2p3 .d14 1s2 =r 1s2 2s2 2p3 . e en than this.p3 .1. may actually ha e a lower energy than those in the pre ious le el.p3 .s2 .s2 ..s2 . C 1s2 2s2 2p3 .4 .p.s2 .of any atom in that period.d14 1s1 Fn 1s2 2s2 2p3 . and scandium shows that the situation is a little more in ol ed. 2. Inter !an/in/ ener/+ le. the energy le el of f:orbitals is always 2 behind the period number..d2 1s1 Mn 1s2 2s2 2p3 . The .s2 .p3 .s2 .p3 .

=oth nuclear charge and the filling of inner shells ha e a great effect on orbital energies as shown in &%'.. 2.G.2.d orbital +section 2. The changeo er in relati e energies of the . the 1s electrons actually participate in bonding more readily than the .%n scandium.3.than the .d orbitals. .. *o far this seems consistent. suggesting that the 1s orbital is at a higher energy than the .d orbitals appear to ha e a higher energy than the 1s orbitals in potassium and calcium.d electrons. the 1s electrons ha e lower ionisation energies +section 3. %n fact this is the case.iii. ..-. two of the three highest energy electrons are found in the 1s orbital and the third is found in the .d orbital.. but in scandium and titanium +and the other transition elements. All we are saying is that the .d electron.owe er. in titanium. Moreo er. they repel 1s electrons away from the attraction of the nucleus.the 1s orbitals appear to ha e a higher energy than the .. =ut we ha e come a long way without mentioning electrostatic attraction.d and 1s orbitals is much easier to understand in terms of a model which emphasises electrostatic forces rather than energy5 as soon as electrons are attracted into .d orbitals.

0. it is the position in the periodic table which should be remembered. group %D +atomic number 24-5 i) Atomi n"m#er5 *trictly spea(ing. ta(e the element in period 2. MORE IN1ORMATION 1ROM THE PERIODIC TA)*E 2. position in the periodic table is deduced from atomic number. Atomic number can then be wor(ed out from position in the table. by counting. &or e)ample. T!ere i% more in$ormation that can be deduced from atomic number. %t is therefore found to be 24 in this e)ample. but in practice.2.1. using an understanding of the periodic table.2. .

... %t is ob iously 1 in this e)ample.. to 1E-. i.....ii) P!+%i al 'ro'ertie%5 These too depend on electron configuration.. 2.ii) N"m#er o$ %!ell%5 The period number immediately gi es the number of energy le els. The relati e atomic mass is also directly rele ant to physical properties. . .iii) Relati.e atomi ma%%5 This can be roughly estimated once the atomic number has been deduced. .. but e en this can be roughly estimated5 .) O"ter ele tron on$i/"ration5 An understanding of the periodic layout +&%'. e en these properties may be deduced +chapters 1..i) C!emi al 'ro'ertie%5 *ince so many chemical properties depend on the number of outer electrons and the number of inner shells.The rest of the electronic structure is also easily deduced from an understanding of the periodic table$s layout5 . The basis of the estimation is as follows. neutrons are needed in the nucleus to stabilise it.2. %t is ob iously 2 in this e)ample iii) N"m#er o$ o"ter ele tron%5 The group number immediately gi es the number of outer electrons. . i .ydrogen has a sole proton in its only stable nucleus. and the number of the highest energy le el +outer shell-..immediately indicates that the outer electron configuration in this e)ample is5 2s2 2p2. &rom helium onwards. and after bismuth +atomic number E.no number of neutrons will produce a stable nucleus.

.............. for our e)ample element which has an atomic number of 245 2 ...... .... 2:G......................"pg-...... whereas fi e would be needed to (eep four protons apart +&%'...................251 for E............ Protons are positi ely charged and therefore repel each other.... A simple model is consistent with this fact... Thin(ing in only two dimensions... 24 ) 1.1...............................251 is linear..2-51...... This gi es 24 protons and 32 neutrons........... we can roughly estimate the number of neutrons in a nucleus from the atomic number.. %n fact this element is tin........ E......51 .... it can be seen that only two neutrons would be needed to (eep two protons apart.The ratio of neutrons5protons needed to stabilise a nucleus increases from 151 for helium....... The small difference is due to the e)istence of isotopes and due to the fact that the @5P ratio does not actually increase linearly +&%'... to about 1.=i @5P... which has a relati e atomic mass of 11E...... ) 4...............1I+24>E........ gi ing an estimated JAM of 112........................e.............g.......E...G.....=i................ @eutrons can be regarded as (eeping them apart...@5P 151.....@5P.- ........24H.......1...................251 ...... 1. 32 neutrons..... %f we assume that the increase in ratio of @5P from 151 to 1.... neutrons .....

unstable isotopes of an element may e)ist if the ratio of neutrons to protons is not appropriate. and to what e)tent does it merely describe it7 2. Ob iously. especially outer electrons. 2.which determines the element$s characteristic properties. the number of protons is the same in all atoms of an element. . E en below an atomic number of E. detailed. 3UESTIONS 1.The JAM of 11E. can you thin( of a case of attraction between opposite charges that does not ultimately depend on attraction between protons and electrons7 Thus to what e)tent does charge difference e)plain the attraction between protons and electrons.. This is predictable because it is the number of protons +and more directly the number of electrons. further draws attention to the fact that atoms of an element may occur as more than one type +isotopes.with differing numbers of neutrons.6escribe an orbital model of the atom which emphasises electrostatic attraction between nuclei and electrons rather than the energies of orbitals. or general than the attraction between a proton and an electron7 &or e)ample.G. This is the starting point of the ne)t chapter.2.6oes the concept of charge describe a property which is more fundamental.

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