Section 2 Electronic Structure of Atoms

Page 1

Section 2
Atomic Spectra

Electronic Structure of Atoms

If sunlight or light from an electric light bulb is formed into a beam by a slit and passed through a prism on to a screen, a rainbow of separated colours is seen. The spectrum of colours is composed of isible light of all wa elengths and is called a continuous spectrum. If the light source is a discharge tube containing a gaseous element, the obser ed spectrum consists of a number of coloured lines on a blac! bac!ground. The spectrum is called an atomic emission spectrum or line spectrum. All substances gi e emission spectra when they are e"cited in some ways, for e"ample, by the passage of an electric discharge or by a flame. A tube of hydrogen gas which has been e"cited by an electric discharge glows with a reddish#pin! colour. An absorption spectrum is seen when white light $light of all isible wa elengths% is passed through a substance. &lac! lines on a white $or rainbow colours% bac!ground can be seen where light of some wa elengths has been absorbed by the substance. Spectrometers are instruments for iewing emission and absorption spectra.

The Hydrogen Atomic Spectrum

'hen iewed through a spectrometer, the emission spectrum of hydrogen is seen to be a number of separate sets of lines or series of lines. These series of lines are named after the names of their disco erers as shown in the following diagram(

Pfund

Paschen

Balmer

Lyman

The lines in the isible region are called Balmer series. Each line of the spectrum corresponding to a definite wa elength of radiation.

Interpretation of the Hydrogen Spectrum

&ohr put forward his picture of the atom in 1)1* to e"plain the line spectra of atomic hydrogen. +e related the lines in the atomic spectra to changes in the energies of electrons in atoms. +e maintained that an electron mo ing in an orbit of an atom could only ha e certain fi"ed alues. These were called discrete or ,uanti-ed le els. An electron mo ing in one of these stable orbits does not emit energy. An electron could .ump from one energy le el to another by emitting or absorbing a fi"ed amount of energy. This was called a ,uantum of energy. n/* n/2 n/1 excited state excitation
emit fixed amount of energy emission or line spectrum

$absorb fi"ed amount of energy% absorption spectrum

n/1

ground state

An electron in its lowest energy le el was said to be in its ground state. Electrons in higher energy le els were said to be in e"ited states. The transition of an electron to a higher energy le el was called an excitation. If an atom absorbs a photon $a ,uantum of light energy%, it can promote an electron from an inner orbit $lower energy le el% to an outer orbit $higher energy le el%. If sufficient photons are absorbed, a blac! line appears in the absorption spectrum. Since only a line spectrum is produced, it indicates that only certain higher energy le els are allowed for the electron in the hydrogen atom. $If any energy le els were allowed, the emission spectrum will be continuous.% According to the ,uantum theory, the energy contained in a photon of light of fre,uency is h , h being Planc!0s constant. 1or an electron to mo e from an orbit of energy E 1 to one of energy E2, the light absorbed must ha e a fre,uency gi en by Planck's equation(

Section 2 Electronic Structure of Atoms

h / Plan!2s constant

Page 2

E2 # E1 / E / h /

hc

c / speed of light / wa elength of lines in spectrum

In an electric discharge, the hydrogen atoms recei e energy due to collision. The energy absorbed by the atom e"cites the electron to a state of higher energy, this is the excited state. The e"cited atom will emit its e"cess energy and returns to the ground state by a single or a series of transitions in which the electron drops to states of lower energies. In each transition, electromagnetic radiation is emitted with fre,uency depends on the energy lost by the electron. 1or e"ample, the Lyman series in hydrogen spectrum is caused by electron transitions from higher energy le els to the ground state. n/ n/3 n/4 n/5 Pfund series n/6 &rac!ett series n/* Paschen series n/2 &almer series n/1 7yman series The atoms of each elements ha e a uni,ue arrangement of electrons with definite energy le els. 'hen the atom is e"cited, electrons are brought to higher energy le els. As the electrons return to lower energy le els, the atom emits radiation of definite wa elengths. This results in a uni,ue emission spectrum which can pro ide useful information about the atom.

1.

a%

b%

In what way are the other series in the hydrogen spectrum similar to the &almer series 8 999999999999999999999999999999999999999999999999999999999999999999 999999999999999999999999999999999999999999999999999999999999999999 :i e a simple e"planation for this similarity, in terms of energy le els. 999999999999999999999999999999999999999999999999999999999999999999 999999999999999999999999999999999999999999999999999999999999999999 999999999999999999999999999999999999999999999999999999999999999999

Summary of Bohr's Theory 1. 2. E"tranuclear electrons can only mo e in certain or emit energy.

stationary $stable% orbits. In these orbits, they do not absorb

The stable state corresponds to certain energy, i.e. an electron in certain stable state has a certain energy E. The emission of energy was caused by mo ement of an electron from one stationary orbit to another of lower energy. 'hile absorption is the re erse. &y Planc!0s e,uation, an electron in state of E 1 to another state of E2 $E1 ; E2 %, then the energy emitted $ E % will be h .

*.

Limitation of Bohr's Theory &ohr0s theory failed to account for the spectrum of other elements and failed to account for the fact that when spectral lines of an emission spectrum is e"amined by a spectroscope of high resol ing power, each line is found to consist of a number of composite lines $fine structure of the spectrum%.

Ionization Energy

Section 2 Electronic Structure of Atoms Ioni ation energy is the energy re,uired to remo e an electron in the ground state $n / 1% from an isolated gaseous atom of an element to an infinite distance $n / % from the nucleus. i.e. < $g% <= $g% = e # E / 1st I.E.

Page *

The energy re,uired to remo e the ne"t electron from the positi ely charged ion is called the second ioni-ation energy of this element. i.e. i.e. <= $g% <2= $g% = e # <*= $g% = e # E / 2nd I.E. E / *rd I.E.

<2= $g%

The alues of successi e I. E. increase in this order( 1st I.E. > 2nd I.E. > *rd I.E.

The reasons for this are( 1. 2. E ery time an electron is remo ed, the resulting ion carries one more positi e charge and e"erts a stronger electrostatic attraction on the subse,uent electron to be remo ed. Initially the outer electrons are remo ed, but later on the electrons to be remo ed come from lower energy le els $i.e. closer to the nucleus% so the coulombic attraction is greater.

E"ample 1 # The Successi e I. E. ?ur e of Sodium Since the successi!e ioni ation energies increase significantly in magnitude, it is more con enient to plot them in logarithmic scale.

log I. E.

@umber of electrons remo ed

1rom the graph, we could see that there is 1 electron which is the least firmly bounded by the nucleus . And then followed by A electrons of more firmly held by the nucleus. 2 electrons are held most firmly by the nucleus. And this graph shows that there are * occupied shells in sodium. Therefore the study of successi!e I" #" cur!es also support the iew that electrons are arranged in different shells around the nucleus.

2.

'hich series of lines in the hydrogen emission spectrum would be suitable for determining its ioni-ation energy 8 :i e a reason for your answer. _____________________________________________________________________ _____________________________________________________________________ _____________________________________________________________________ _____________________________________________________________________ _____________________________________________________________________

Shells and Sub-shells

Section 2 Electronic Structure of Atoms #!idence for sub$shells of electrons from first ioni ation energy 1st ioni-ation energy B !Cmol#1

Page 6

Atomic number There is a general increase in the first ioni-ation energies across the period, but some regular dips. Shells and sub$shells Electrons mo e around the nucleus. The regions in which the electrons mo e are called shells. There are many shells. These electron shells ha e different energy states. 'ithin each principal shell, sub#shells of slightly different in energy le els are also present. The first shell can ha e one sub#shell $1s%, the second shell can ha e two sub#shells $ 2s and 2p% while the third shell can ha e three sub#shells $*s, *p and *d%. The fourth shell can ha e four sub#shells $6s, 6p, 6d, 6f%. The relati e energies of the shells and sub#shells $up to 6p% can be illustrated as follows( Shells $n/1,2,*,6,...% Energy 6th shell *rd shell *s 2p 2nd shell 2s *d 6s *p Sub$shells $s#,p#,d#,f#%
6f 6d

6p

1st shell

1s

Atomic Orbitals
In 1)26, a 1rench Physicist 7ouis de &roglie postulated that matter has both particle and wa e properties. 1or the case of an electron, this postulate was later confirmed by the e"periments performed by ?. Da isson with his partner 7. :ermer and by :.P. Thomson. 'hen they passed a beam of electrons through a crystal and through a gold foil, they obtained a diffraction pattern on a screen similar to that obser ed when "#ray was used. This piece of e idence demonstrated that electrons do indeed possess wave properties. 1ollowing this, studies in wa e mechanics ha e shown that electrons are not locali-ed in fi"ed orbits, and as a matter of fact, we can only describe the location of an electron in terms of the probability of finding it in a certain position at any time. Suppose a photograph of the electron of hydrogen could be ta!en at any instant, and a second photograph ta!en at an instant later when the electron would occupy a different position. <illions of such photographs superimposed would generate an electron density diagram shows in figure 1.

The electron spend some time at some far distance from the nucleus but for most of the time it is close to the nucleus. The dot density represents the probability of finding the electron. The region in which the electron might ha e any probability of e"isting is called an orbital. An electron can no longer said to occupy a specific, limited orbit. %tomic orbitals are the regions in which there is the greatest probability of finding particular electrons, although the electrons are not confined to these regions. The distribution of 1s electron is symmetrical around the nucleus, in form of sphere, but this sphere has no e"act radius. In practice, a radius is chosen in such a way that the sphere contain the olume within which there is )EF chance of finding the electron, i.e. the orbitals.

Section 2 Electronic Structure of Atoms Page 5 1or orbitals of higher energy states, for e"ample, p orbitals, they are no longer spherically in shape. The shape of some orbitals are shown below(

y " s orbital
" p orbital "

" y p orbital y p orbital -

*.

Electronic Configuration of Atoms

The arrangement of electrons in atoms is go erned by three rules. Hule 1( The aufbau principle. The principle states that the electrons are arranged so that the energy is at a minimum. +ence the lowest energy orbitals are always filled first. Hule 2( The Pauli #xclusion Principle. $a% no orbital can contain more than two electrons and $b% if two electrons occupy the same orbital, they must ha e opposite spins. Hule *( &und's 'ule. This states that the orbitals of a sub#shell must be occupied singly and with parallel spins before they can be occupied in pairs. According to +und0s Hule, electrons do not pair in an orbital until all the other orbitals in the subshell ha e been occupied by a single electron. 1or e"ample( @itrogen $I / 3% obeys +und0s Hule by accommodating the three 2p electrons in different orbitals with the same spin. 1s @( 9999999999999999999999999999999999999999999999999999999999999999999999999999999999999 +' B ?' &y using electron#in#bo" notation, gi e the electron configuration of the first 1A elements $up to Argon%. 9999999999999999999999999999999999999999999999999999999999999999999999999999999999999 The filling in of subshells by electrons are according to their energy. 2s 2p

"
a% ii% b% a set of three p#orbitals 8 ii% a p#orbital .

+ow many electrons can be held in i% an s#orbitals,

Gse one word in each case to describe the shape of i% an s#orbital,

Section 2 Electronic Structure of Atoms Period ( The first shell is being filled, this shell can accommodate two electrons only, i.e. the 1s orbital.

Page 4

Period ) The second shell is being filled. This shell can accommodate A electrons by the 2s $which can accommodate 2 electrons% and the 2p $which can accommodate a total of 4 electrons%.

Period * The filling of the third shell gi e rise to elements in Period *. The third shell can accommodate a total of 1A electrons by the *s, *p and *d orbitals. &ut unli!e the first two periods, Period * and the *rd shell are not completed at the same time. Period * comprise the filling of *s and *p orbitals. The *d orbitals are not filled in Period * because the energy of these orbitals are higher than that of 6s. And once the filling of 6s signify the start of the fourth period, therefore Period * and the *rd shell are not completed at the same time.

Period + In the first two elements, the 6s orbital is filled. Starting from Scandium, Sc $I / 21%, the electrons start to go to the *d orbitals because they are now the lowest energy orbitals a ailable. The filling of the *d orbitals gi e rise to the first transition series $a total of 1E elements%. After the completion of the *d orbitals, the ne"t electron will go to the 6p and gi e rise to the elements up to Jrypton, i.e. the 6p orbitals are filled. The 6th shell and Period 6 are also not completed at the same time. $'hich orbitals in the fourth shell are still empty8% 9999999999999999999999999999999999999999999999999999999999999999999999999999999999999 +' B ?' &y using electron#in#bo" notation, gi e the electron configuration of the ne"t 1A elements $Potassium to Jrypton%. 9999999999999999999999999999999999999999999999999999999999999999999999999999999999999 Summary The order of energy of different orbitals and the order of filling of orbitals are listed below(
1 1s 2s *s 6s 5s 4s 3s 2p *p 6p 5p 4p 3p *d 6d 5d 4d 6f 5f 2 * 6 5 4 3 A

6.

&y using electron#in#bo" notation, gi e the electron configuration of( 1s +( +e( 7i( &e( &( ?( @(K L( 2s 2p *s *p

Section 2 Electronic Structure of Atoms 1( @e( @a( <g( Al( Si( P( S( ?l( Ar( *d J(K ?a(K Sc( Ti( O( ?r(K <n( 1e( ?o( @i( ?u(K In( :a( :e( As( Se( &r( Jr( M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N M N 6s 6p

Page 3

5.

Gse the s , p , d , f notation to write the electron configuration for a% nitrogen, b% c% chromium, copper.

4.

'rite down the orbitals which are filled in going across the si"th periods.

The Periodic Table and the atomic properties of the elements

The Periodic Table

Section 2 Electronic Structure of Atoms Page A The Periodic Table has four areas called s#, p#, d# and f#bloc!. Elements in ol ing outer orbitals of solely s and p electrons lie either in the s$ or p$blocks of the Periodic Table. The central region of the table, corresponding to the filling of d orbitals of the elements are !nown as d$block elements. There are two series of elements at the bottom of the Periodic Table corresponding to the filling of 6f and 5f orbitals are !nown as the f$block elements. I II s-block 1s 2 3 4 5 6 7 s s s s s s III IO d-block O OI OII p-block 2p 3p 4p 5p 6p E 1s

* ** f-block

3d 4d 5d 6d

1s 1s

* **

4f 5f

1s 1s

%tomic radii The electron cloud of any atom has no definite limit, thus the si-e of an atom cannot be defined simply and uni,uely. In the case of atoms forming co alent molecules, co alent radii are used. 1or e"ample chlorine, the co alent radius of chlorine is defined as half the internuclear distance between two co alently bonded atoms in the chlorine molecule. In the case of metals, metallic radii are used. The metallic radius is defined as half the internuclear distance in the metallic crystal. The atomic radii of the elements in Period II and III are gi en below( Period II Period III 7i E.12* @a E.154 &e E.EA) <g E.1*4 & E.EA2 Al E.125 ? E.E33 Si E.113 @ E.E3E P E.11E L E.E44 S E.1E6 1 E.E46 ?l E.E))

Two general periodic trends are found( $i% the si-e decreases along a period P
Across the period, each element ac,uires an additional proton in its nucleus, together with an additional electron in its outermost shell. Since the added electron is placed in the same ,uantum shell, it is only shielded wea!ly by other electrons in that shell from the e"tra positi e charge on the nucleus. +ence the effecti!e nuclear charge is said to be increased. Therefore , the atomic radius decreases.

and $ii% the si-e increases down a group.

Down the group, the number of electron shells increases and hence the atomic si-e increases.

Ioni ation #nergy Variation of I. . for a !roup 1st Ioni-ation energy B !Cmol#1 @e

1 @ &e & 7i @a Atomic number Ln passing down the group, the first ioni-ation energy generally decrease. <g Al L ? Si P S ?l Ar

Section 2 Electronic Structure of Atoms

1or each element down the :roup, # the outermost electron which is to be remo ed is shielded by an inner shell of electrons. good shielding $screening% effect from the e"tra positi e charge effecti e nuclear charge decrease # atomic si-e increases ma!ing the nucleus more difficult to hold this outermost electron firmly. more easily to lose the outermost electron +ence, I. E. decreases down the group.

Page )

Variation of I. . for a "#riod (st I"#" +e @e Ar ?l P <g Al @a J Ln passing along a period, there is a general increase in first ioni-ation energy.
# # # # increase in effecti e nuclear charge across the period causing a decrease in atomic radius electron cloud becomes closer to the nucleus it becomes more difficult to lose an electron

+ @ &e & 7i L ?

Si

S ?a

%tomic number

+owe er, the plot of I.E. along a short period has a typical saw#tooth shape $small drops within the general rise%. $a% In t&# 2nd p#riod' t&# 1st I. . of boron$(% is lo)#r t&an t&at of b#ryllium$(#%. In t&# 3rd p#riod' t&# 1st I. . of aluminium$*l% is lo)#r t&an t&at of ma+n#sium$,+%.
1or &e B <g, the electron remo ed is in a completely filled 2s B *s orbital and this is a relati ely stable configuration. Therefore this re,uires more energy. 1or & B Al, the first electron remo ed is an unpaired 2p B *p electron since the electronic configuration is not a particularly stable one, thus re,uires less energy than that of &e B <g. <oreo er, the electron remo ed in & B Al is an p electron which is less firmly held by the nucleus than the s electron as in case of &e B <g.

$b%

In t&# 2nd p#riod' t&# 1st I. . of o-y+#n$.% is lo)#r t&an t&at of nitro+#n$/%. In t&# 3rd p#riod' t&# 1st I. . of sulp&ur$S% is lo)#r t&an t&at of p&osp&orus$"%.
@itrogen has a stable electronic configuration of 1s 2, 2s2, 2p"1, 2py1, 2p-1, while in case of o"ygen, the electron configuration is 1s2, 2s2, 2p"2, 2py1, 2p-1. @itrogen has a half#filled p#orbitals which has extra stability. Therefore it re,uires more energy to remo e one electron form nitrogen as this will brea! the stable electronic configuration.

000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000000 Summary ,actors affecting the !alues of ioni ation energy 1. 2. The magnitude of the nuclear The screening
# #

charge.

effect of the underlying electrons.

electrons added to the same ,uantum shell has poor screening $shielding% effect on other electrons from the positi e nuclear attraction. electrons added to the inner ,uantum shell has good screening $shielding% effect on other electrons from the positi e nuclear attraction.

*. 6.

The distance of the outermost electron from the nucleus $atomic radius%. The shape of the orbital of the electron in ol ed.
# Gsually s electrons are more firmly bounded than p electrons which in turn more firmly bounded than d electrons.

5.

Some stable
#

electronic

Section 2 Electronic Structure of Atoms configurations re,uire a greater energy to brea!.

Page 1E

1or e"ample, a fully filled shell or a half#filled shell has e"tra#stability.

3.

a%

'rite e,uations to show the first, second and third ioni-ation energies of magnesium.

b%

'ould you e"pect the alues of these ioni-ation energies to increase or decrease, in the order( 1st, 2nd, *rd 8

c% E"plain your answer to $b%. _____________________________________________________________________ _____________________________________________________________________ _____________________________________________________________________

#nd of Section #xercise

1.

The following table shows the first si" ioni-ation energy alues for each of four conser ati e elements in the Periodic Table. Ioni-ation energy $!C mol#1% Element 1irst Second Third 1ourth 1ifth Si"th ' 124E 2*EE *AEE 52EE 45EE )*EE Q 152E 23EE *)EE 5AEE 32EE AAEE R 62E *1EE 66EE 5)EE AEEE )4EE I 5)E 11EE 6)EE 45EE A1EE 1E5EE a% is B are noble gas$es%, b% will form an ion with a single positi e charge, c% will form an ion with a double positi e charge. The first and second ioni-ation energies of potassium and calcium are gi en below( Ioni-ation energy Potassium ?alcium #1 61) 5)E lst ioni-ation energy B !C mol 2nd ioni-ation energy B !C mol#1 Account for the differences in ioni-ation energies. *E52 1165 $6 mar!s% $A)2A2$c%%

$ii%

Arrange the following elements in order of increasing first ioni-ation energy ( 1, @e and @a. E"plain your order. $iii% Describe and e"plain the ariation of the successi e ioni-ation energies of potassium. $S!etch a plot of successi e I.E. $in log scale%% $5 mar!s% $)22A1$a%%

Section 2 Electronic Structure of Atoms

Page 11

%nswer to #xercise 1. $a% ' or Q $b% R $c% I $A)2A2c% The first ioni-ation energy of an atom is always smaller than the second ioni-ation energy. The first ioni-ation energy of ?a is higher than that of J because ?a has a larger nuclear charge $I / 2E% than J $I / 1)% and the two 6s electrons in ?a do not shield each other strongly. +owe er , the re erse holds for the second ioni-ation energy because the *p electron in J is much closer to the nucleus than the second 6s electron in ?a. $6 mar!s% Also , the remo al of second electron of J has to brea! the completely filled *p # orbital and more energy is re,uired $for 2nd I.E. of J% in order to o ercome the e"tra # stability of completely filled orbital.

2.

*.

$)22A1a% $ii% @a > 1 > @e $1% @a has the least I.E. because there is a single *s # electron is not strongly attracted towards the nucleus and losing it would accomplish the completed s# and p# orbital status. It is for this reason that an electron in @e re,uires the highest I.E. To lose an electron means that the 1 atom would mo e further away from the completed s# and p# orbital status and this re,uires a relati ely high I.E. $1% $iii% There is a gradual increase in the successi e ioni-ation energies in general because the nucleus becomes effecti ely more positi ely # charged as each electron is being lost. The increase is greatest when the 2nd electron are being ioni-ed , suggesting the 2nd electron is closer to the nucleus than the first. Similar greater but less abrupt I.E. 2s occur when the 1Eth and 1Ath electrons are being ioni-ed. Successi e I. E.

Section 2 Electronic Structure of Atoms

Page 12

log I.E.

no. of electron remo ed 2 1E 1A

Past Paper )5IA 1$a% $i% $ii% The first four successi e ioni-ation energies of an element A are 53A, 1A13, 2364 and 1EA1* !C mol# 1 respecti ely. To which group in the Periodic Table does A belong8 The relati e atomic mass of bromine is 3).)E. It has two isotopes with mass number 3) and A1. ?alculate the relati e abundance of each isotope. $* mar!s% )5IA 1$b% $i% $ii% 'hat can you deduce from the fact that the spectral lines in the atomic emission spectrum of hydrogen are not e,ually spaced8 $1 mar!% In the atomic emission spectrum of hydrogen, the con ergence limit for the 7yman series occurs at *.235 1E15 +-. ?alculate the ioni-ation energy of hydrogen, in !C mol#1. $Planc! constant, h / 4.424 1E#*6 Cs P A ogadro constant, 7 / 4.E2* 1E2* mol#1% $2 mar!s%

)2IA

2$c% :i e the shape of 1s#orbital and comment on its physical significance. $2 mar!s%

9999999999999999999999999999999999999999999999999999999999999999999999999999999999999 -aking Scheme )5IA 1$a% $i% $ii% :roup III Assuming 3)&r ( A1&r 3)" = $1 # "%A1 " / " ( $1 # "% / 3).)E / E.55 1 1

Section 2 Electronic Structure of Atoms Abundance of

3)

Page 1*
1 1 2 2

&r
A1

&r

/ 55F / 65F

1$b% $i% $ii%

The energy difference between electron shells in a hydrogen atom are not the same $con erge%. 1 I. E. / h / 4.424 " 1E#*6 " *.235 " 1E15 1 / 1.*E3 " 1E4 C mol#1 $1*E3 !C mol#1% B $1*E5 # 1*1E !C mol#1% 1 $ 2 mar! for numerical answer P 1 1E2*

"

4.E2*

"

mar!

for

unit%

)2IA

2$c% 1s # orbital is spherical. Physical significance # # The probability of finding an electron at 1 orbital. 2

arious points in space is called an

1or a gi en 1s # orbital, the region of highest probability of finding the electron, say )EF of the charge distribution is pictorially represented by a single surface along which the probability of finding the electron is constant.
1 2

They should be thought of as shapes with fu--y and indistinct edges, li!e a 1 cloud. 2