,.

AndersonJunior College
Ghemistry Lectures 2004

ATOMICSTRUCTURE
Objectives
shouldbe ableto:
Candidates
(a)
identifyand describeprotons,neutronsand electronsin termsof their relative
chargesand relativemasses.
(b)
deducethe behaviourof beamsof protons,neutronsand electronsin both
electricand magneticfields.
(c)
describethe distributionof massand chargeswithinan atom.
(d) deducethe numberofprotons,neutronsandelectronspresentin bothatoms
and ionsgivenprotonand nucleonnumbers(andcharge).
(i)
(e)
describethe contributionof protonsand rieutronsto atomicnucleiin terms
of protonnumberand nucleonnumber.
(ii)
betweenisotopeson basisof differentnumbersof neutrons
distinguish
present.
(f)
describethe numberand relativeenergiesof the s, p andd orbitalsfor the
principalquantumnumbers1,2 and3 and alsothe 4s and4p orbitals.
(S) describethe shapesof s and p orbitals.
of atomsand ionsgiventhe protonnumber
(h) statethe electronic
configuration
(andcharge).
energiesof elements(see
the ionisation
(i)
(i)
explainthe factorsinfluencing
DataBooklet);
(ii)
explainthe trendsin ionisationenergiesacrossa periodand downa
groupof the PeriodicTable.
(j)
deducethe electronicconfigurationsof elementsfrom successiveionisation
energydata.
(k)
interpretsuccessiveionisationenergydata of an elementin termsof the position
of thatelementwithinthe PeriodicTable.

References
1
2
3
2
4
5
6

The CentralScience(8h edition).Brown,LeMay,Burster.(Chapter

Chemistry,
2 ,6)
(2noedition).ChrisConoleyand PhilHills.(Chapter3)
Chemistry
Ann & PatrickFullick.(Chapter1.4)
Chemistry.
ChemistryIn Context(5h edition).Hitland Holman(Chapters5, 6)
JGRBriggs.(Chapter2)
LongmanA-LevelCoursein Chemistry.
(Chapter2)
(4'
E.N.
Ramsden.
A-LevelChemistry edition).
(3'edition).Olmsted& Williams.(Chapters6, 7)
Chemistry

chai/atomicstructure/2004

Atoms
. smallestelectrically
of an element
neutralcomponents
. possessall the chemicalproperties
of the element
o an atomcomposesof 3 fundamentalsubatomicparticles:

+1.602 x 10-

-1.602x 10o the quantity1.602x1O-ts

C is calledthe etectroniccharge
. atOmS haVe

no

net electricalcharge

(5A)]
(1A) < diameter< 5x'10-10m
atomsare extremelysmall[1x10-10m
atomshaveextremelysmallmasses
a unitcalledatomic mass unit ( amu ) is usedto expresssuchsmallmassesin
gram
1 amu = 1.66054x10-2ag

5.486x10

protonsand neutronsare collectivelycalled--g!gg

in the
all the massof the atomis concentrated
electronsresidein the restofthe space

a'ov"a

n^tl?.rr
the nucleus

electronsare attractedto the protonsin the nucleusby ete*.alot. kuos

the protonsand neutronsin nucleusare drawnvery closetogetherby extremeforces
theseforcesare only effectiveover a very shortrangebecausethey do not pull the
otherelectronsintothe nucleus

chai/atomicstructure/2004

o manymore subatomicparticlesare now knownto exist(eg. the positrons'the

neutrinos,the hyperons,etc.),but theseare not generallyconsideredin chemistry
Behaviour of protons. neutrons and electrons in:
(a) an electric field

beamof protons,
neutrons.electrons

(b) a maqnetic field

beamof protons,
neutronsand electrons

p\
\o'

& ,1& r.

DnHt It
ftd tda
PaT

Atomic Numbers.Mass Numbersand lsotopes

. 'nuclide' appliesto a nucleuswilh a specifiednumberof protonsand neutrons
. Symbolof a nuclide:
A

l=

AtomicNumber

= numberof protonsin the nucleus

= protonnumber

A=

MassNumber

= numberof protonsand neutronsin the nucleus

= nucleonnumber
chai/atomicstruchrrey'2004

. aflatomsof an elementhavethe

3A*

protonnumberin the nucleus

. the specificnumberof protonsis differentfor differentelements

lsotooes
. isotopesare atomsof an elementthat have.the s4w
numberof protons(same
numberof neutrons(differentmassnumber)
atomicnumber)but
&f&ra,'t
. the differentmassnumbersare knownas isotoplc masses

. isotopes
same

CVUii ral

propertiesbut different

rt qs:rat

properties.

Example1

Example2

Pickout
(i)
a pairof isotoPes A on) E
(ii) a pairof ionswhichcamefromthe isotopes s cbr a
(iii) an ionwitha -3 charge D

chai/atomicstructurey'2004

ElectronicStructure of an Atom
. knowledge
is theresultof quantumtheory
of themodematomicstructure
. majordevelopmentof the quantumtheory:
Failureof theory
By the lawsof electromagnetics
. movingelectronswould radiate
and
energycontinuously
decreaseits velocity
. electronswould eventuallyfall
intothe nucleus
. atomwouldcollaose
. atomwouldproducea
continuous
spectrumwhich
the linespectrum
contradict
observed
r contradicted
Heisenberg's
. electronsmovein fixed,
Principlewhichsays
Uncertainty
fixed
and
2. Bohr's
stationaryorbitsof
to determine
that it is imoossible
Theory
definiteenergiesaroundthe
position
precisely
the
and
both
nucleus.
velocity(andhencemomentum)
. electronin any of the
of a particleat the sametime.
does
not
stationarystates
. for complexatoms,eachlinein a
radiateor absorbenergy
linespectrumis madeup of many
e energyis emittedwhen
fine linesclosetogether(high
electronmovesfroma higher
resolution)
energystateto a lowerenergy
state
o energyis absorbedwhen
electronmovesfrom a lower
energystateto a higher
energystate
. electronsmovein circular
orbitsaroundthe nucleus
. electronhas quantizedangular
momentum
. can accountfor the spectral
linesof atomicsoectrumof
hvdroqen
. electronsshowdual nature
J.
of
i.e.they haveproperties
Schrodinge/s both particlesand waves
quantum . mathematical
expressions
mechanics calledSchrodinger
wave
equationsdescribemotionof
an electronin termsof its
energy
. waveequationsstate the
probabilityof findingthe
electronat any particularplace
. cannottell exactlypositionof
an electronat any particular
Postulates
. electronsrotatingaroundthe
1. Rutherford's nucleusat variousdistances
. electronsare preventedfrom
Model
fallingintothe nucleusby
centrifugalforce
Theory

chai/atomicsFucture/2004

moment
. an orbital is the regionin
spacewherean electronis
likelyto be found
. orbitalshavedistinctive
and
shapesand symmetries
an
allowed
each denotes
energystatefor the electron
. orbitalsare describedby 4
quantumnumbers

I
I
I
I

QuantumNumbers
. each electronin an atom is designateda set of &.r

quantumnurnbers

1 PrincipalQuantumnumber(n)
. electronsin an.atomare arrangedin a seriesof shells
. eachshellis givena numberknownas the principalquantumnumbern
. n hasintegralvalues1,2,3,4,...and
determines
the energyof the electron
. the shellnearestthe nucleus(n = 1) hasthe
. shellswith highern have

kqrhv

lo"'(rt

energy

energies

. eachprincipalquantumshellis capableof holding2n2electrons.

eg.

=
n = l,total numberofelectrons

'

n = 2, totalnumberof electrons=

r eachprincipalquantumshellconsistsof differenttypesof subshells

2 SubsidiarvQuantumNumber(l)
(n'1)
. eachsubshellcan be denotedby a subsidiaryquantumnumber,, = 0,1,2,3,..
r the valueof I for subshellis generallydesignatedby the letterss, p, d, f
r differentsubshellswithin a specificquantumshellare associatedwith different
energies,in ascendingorder:

s(p <d <t

. I definesthe shapeof a subshellin the quantumshell

chai/atomicstructure/2004

:,.

P
J

s
P
J

I
eachtypeof subshellcontainsone or moreorbitals ,
3 MaEneticQuantumNumber
can be denotedby a magneticquantumnumber,mr,
a eachorbitalin a subshell
rangingfrom J to +l
the numberof orbitalsis determinedby the typeof subshell

orbitalsthat havethe sameenergyare knownas

eg. the 3 'p'orbitalsare degenerate,
the 5 'd' orbitalsare degenerate,
the 7 'f orbitalsare degenerate.
4 Spin QuantumNumber
a each orbitalcan containa maximumof
spin

orbitals

4c4t2144

efectronswhichare of

owAh

an electronin an atom behavesliketiny magnetwhichspinson its axis,eitherin a

clockwise(usuaflyrepresentedby ll or anti-clockwisedirection(f )
the spinof eachelectroncan be denotedby the quantumnumber,ffig= +lh 67 'y2

chai/atomicstructure/2004

Summarv

Total2

TotalB
p

Pt

2
o

2
P.

P"

2
6

Pv

9.

Total18

2
d

do

dvz

df-f

dl

10

Electronsin Orbitals
. an ofiital is a 3dimensionalvolumeof spacewherethere is a highprobability(more
than95%)of findingan electron.
OrbitalEnerqv
o all the orbitalsin a particular
subshellare at the
. as the principalquantumnumbero
successiveshellsgets
s'"Cf,,

inrrraleg

sard

energylevel

, the energygap between

o as a result,an orbitalin an innershellmay be associatedwith a higherenergylevel

than an orbitalin the ner:tshellout
eg. Relativeenergy: 4s < 3d < 4p

chai/atomicstructure/2004

3d
3p

2p

.r-)

1s
Orbital Shape
. an electronspreadsitselfout aroundthe nucleusas a cloud (electron cloud)
o the shapesof orbitalsreflectthe electron density of this electrcndoud
. regionsof higheleclrondensityhavea high probabilityof findingthe electlon
t s orbital
.

scl*,i taltq

symmetrical about the nucleus

equalprobabilityof findingan electronat a distancerfrom the nucleusin all

directions
s orlritalsin the secondand third shellsonwardshaveregionscalbd 3l,'l-,
where the electrcn density is zero
1s

spac^ f-f.r]
*ra
eLr+mu car.rc+ h S.-1.

cetalh

chai/atomicstructun/2004

the numberof nodesincreases

withincreasing
valuefor the principalquantum
numbern
iv'(.toa

as n increases:the electronis moreand

more likelyto be locatedfartherfrom the nucleus

the size of the orbital

2 p orbitals
. 3 degeneratep orbitals;approximately
perpendicular
to eachother

Juv'Llr{tl

shaped;mutually

eachorbitalconsistsof two lobeswith the atomicnucleuslyingbetweenthem

they are labelled t. ,

f,

Pr

, accordingto their respectiveaxis

eachp orbitalhasa nodeat the nucleusof the atom

the probabilityof findingthe electronis higherfurtherawayfrom the nucleus
Pt

Pv

P,

3 d orbital
. five d degenerateorbitals,
shapes: 4 haveshapeslike3-dimensionsl cl,o*v- lea,lrs
t hbsshapelikea p orbital,and a 'doughnut'of electronsdensityin the xy
plane
dxy

dl,'

l0

chai/atomicstructure/2004

dt

dr'-f

d"r, dn, d,e lie in the aq , Y* and

lobes oointed between the axes

df-f lie in the

1 'l

xz

coordinateplanesrespectively,with the

planeand has its lobespointalongthe x andy axes

z

dz'?
has its majorlobespointingalongthe

axis

Orbitalsize
In any particular
atom
get largerasthevalueof n increases
orbitals

eg.n=3orbitals > n=2 orbitals

all orbitalswiththe sameprincipalquantumnumberare similarin size

eachorbitalbecomessmalleras nuclearchargeincreases.
eg 2s orbitalsteadilydecreasesin size acrossthe secondperiodof the Periodic
Tablefrom Li (z=3)to Ne (z=10)

ElectronsConfiquartion
. electronicconfigurationrefersto the
variousorbitalsin the atomor ion

N*vjh"+o,

CV.+'v"t

amongthe

. normallyappliesto atomsor ionsin the ground state ( i.e. lowestpossibleenergy

levelavailableto it )
o electronsare arrangedaccordingto a set of rules:
1 The Aufbau principle f 0"1rrr* - rt r.truprcl.
. whenformulatingthe electronicconfigurationof a multi-electron
atom,protonsare
are
added
to
orbitals
in
order
of
nucleus
and
electrons
the
addedto the
o this meansthat electronsare accommodatedin the orbitalsof
energyfirst
ll

hr^xrt

chai/atomicstructure/2004

2 Pauli Exclusion Principle

a no two electronsin any atom may have the same set of quantumnumbers
a

electronscan occupythe sameorbital,and in orderto do

this impliesthat only 2
opprclt+,
spln"
so, they must have

3 Hund's Rules
whenfillingdegenerateorbitals,electronsoccupythese orbitals
and with
spin beforeany pairingoccurs
o arallrr

5rr,'413

o electronstend to avoidbeingin the sameorbitaldue to

Writing the electronic configuration
o severalways of denotingthe electronicconfigurationof an atom or ion of an element
include:
1 using boxes
eg. 6C

|ll 4 Vl |tl1 Vl

f-tT1Tl

lr

eg.

roS

l'tv
I
l1vl
tl
tl
1J

Wry4 wT+q
ltll v l

2?

t2

3P

chai,/atomicstrucbre/2004

enerqv levgl diaqrams

e g .rsA l
3s

1v

2s

4v

1s

4v

c
c

3p

2p

1v

4l/

4y

s. D. d. f notation
e s.
,

b')5'
n?s "r7 e
1,

4h
ton

l r-)g) 2 ? ' 3 t '

,,st

| 3')s

rcl

t ,f r 3s- 3p' ts '

Shorthandnotation

Ca

Noblegasconfiguration
rer
it
tl .

t'
f^rr1as-sP

ft'l rsl

,S tl l o

2P

h"

ls " 2 s ' lp L 3 e ' 3 r s

w,

*&rcctronic atomslioos

o atomsor ionsthathavethesamenumberof electronsaresaidto be isoelectronic

eg'

N o .r

l s 1 2 s'2 ,p g

roNe

ls"2s'?r

q ?-

l s , 1s ' 2pt

Excited state elec'tronconfiquratlon.

o ground state configurafionis the

xo}l

ttrul!

anangementof electrcns

r when an atom absorbsl'tghtor is bombardedby energeticelectrons,it can gain

enerqvto reachan excitedstate
'v'zt'vv*
I.'

chai/atomicstruoture./2004

. electronscan moveto a higherenergystateand assumea new electronic

configuration
o excitedatomsare
configuration
o gnly otr

r. .l+alol'

and spontaneouslyretumto the groundstate

groundstateexistsbut there can be

eg.

g.t,b eE ig
atrt.a

o X.

a+ &Fo{..1D
t+*a

r la ( ?o..rf +.,L )

excitedstates

#_-_(ne t","

rv' 4r4

q{.-

4o..fa ror,,rl1 )

ercitJ

at
1

".4s+etta

cf a*

ls? !1 1 p 0 3 s ,

N4 [erc,*trt.r{a+,)

tsr )3':,

,
-d

g!

ls " 2s, 3ps zn "

ElectronicConfiqurationof Elementsin the PeriodicTable

t-l"t
T l o .t

2s

1s

3s
4s
5s

3d
4d

2p
3p
40
5D

6s
7s

5d

6o-

6d

fi a l

ya

'r '

Periodic Tableshowingthe grouping of elementsaccoiding to the type of orbital being

filled with electrons

In the periodictable,
. elementsareranged in orderof their

a*o*t1*

1Oalo.)

. elementsin the'samePeriodhaveelectronsoccupyingthe same

shell

- numbers
o,rb'"r"l-t

srh,
. elementsin the sameGrouphavethe
numberof valenceelectrons
electronicconfigurationin the valence(outermost)
and thus,
ia'n'Q
orbitalsin theiratoms

l4

chai/atomicstructure/2004

Valenceshell electronicconfiguration

Group

il
^9

ill

.t
ts 'n?

IV

.-l - trP

ns nf

VI

ng'nP'

vtl

ng" f5

vill

.b
nS - nP

Electronicconfigurationsof first row transitionelements:

filledd orbitals
. similarelectronicconfigurations
with
pr,vt'?lls
o all have4s23d'1 x = 1 to 10 ) exceptfor Cr and Cu.
Element

AtomicNo.

Sc

21

Ti

22
23

ElectronicConfiguration
f A rl

It"l
rA"l

+s2 3Jr

qs-gJ'
4 s ' ill

Cr

24

EA'l +s'gJ 5

Mn

25

EAv)I s7 3) e

Fe

26

fA'l +:'sJ(

Co

27

g a "f + s* 3 Ja

Ni

28

Cu

ZJ

Zn

an

fl" J+ .' 3 Jt

f*.J 'ts ' 3J'"

fa']+"a3Jro

l5

chai,/atomicslructur/2004

lonisation Energv
. Definition
Thefirstionisation
energyof an elementis the energyneededto removeonemole
of electronfromonemoleof gaseousatomsof the elementto formonemoleof
singlychargedgaseouscations.
X( S) - tX t(S )

first ionisationenergy

* t

o ionisationenergyincreaseswith

in effectivenuclear charge

tnca OS

r effectivenuclearchargeis the actualchargeexperiencedby the electrons,different

from nuclearcharge(atomicnumber)
Factors affecting the effective nuclear charse
1 nuclearcharqe
*
. increases
withthe numberof
?,o+o

(indicatedby the atomicnumber)

s+-s.^{v +W a*.r|'q.,
. the largerthe nuclearcharge,the
nucleusand the electron(providedotherfactorsremainthe same)

betweenthe

2 Shieldinsor screeninqeffectof inner electrons

a eachelectron
attractedto the nucleusand
in a multi-electron
atomis simultaneously
repelledby the otherelectrons
shieldingis the phenomenonwhereattractionbetweenany givenelectronand the
repulsion
by the electron-electron
nucleusis
electrons
with an increasein the numberof
shieldingincreases
. increasein shieldingresultsin

& t n1^st

shells
in effectivenuclearcharoe
6 rrr,rtt""t '! rL
^+'aa.h\
aPtrls?r"
l

relativeshieldinqand effectivenuclearcharqe:

e N,tw

- quantumshellsof smallern are more

highern

shieldsthan those with

for a givenshelln, the screeningabilitydecreasesin the order: s > p >J > f

hence,for a givenshell n, effectivenuclearchargefor:
s electrons >

.Lr*'*lr

lo

ekr{'r^r

>

ekc+'e,ng

chai/atomicstruchrre/2004

First l.E./ kJ mol'l

He

Ne

2000
z2p3
1-- I tz 3
0.

1 ,2 2 t:

zpf
1500

Kr

t
I s' L r
l s')s-Pr
1000

t' 2 s' 3 P6 3 r'

500

Li

30

10

40

50

Atomicnumber

acrossa period
- nuclearcharge

ir,o trfaJr3

- screeningeffect remains

=>

'th f /f aJJ

effectivenuclearcharge

energy
- hence,ionisation
elements

qxhnn4d

rtl*i(|3

'r^(?l'l

cross a periodfor successive

- noblegase has the highestfirst ionisationenergyand Group I elementhas the

lowest
downa group
- nuclearcharge

ira r.{.4:

11

chai/atomicstructure./2004

- screeningeffectincreases

*9n

=> effectivenuclearcharge

i n Otta

c \.'

'Y

)Q c N a,*t

At t nat/J

- hence,ionisationenergy
for the d and f blockelements
- increasein nuclearchargeis
and f orbitals

by increasein screeningfrom the d

"lf'<*

&,"1s

- ionisationenergyis

hd V 1'

"v

r,oy.siq'r|

T ,E

Aua eloncS
rTull

{oo

Hiqherlonisations
. Definition
The secondionisationenerqvof an elementis the energyneededto removeone
moleof electronsfrom one moleof singlychargedgaseouscationsto form one mole
of doublychargedgaseouscations.
X. (g) -+ X'- (g) *

secondionisationenergy

"-

. similarly,
Xt* (g) *

xt* (g)
:

energy
thirdionisation

"-

X(*t)(g) + Xn*(g; + s-

.*

|
)

nth ionisation
energy

o,.,...
c+

'.

o.{
+r.r.t

o successive ionisation energies referto energiesrequiredto removeelectrons

from a gaseousatom
al\" a,JN
nr
o an electronlost in ionisationis alwavsremovedfrom the

arla*

. successiveionisationbecomesmoredifficultas cationcharge
- the numberof electrons

't

shell

lv\ (i.!aJ?J

Aro,$u'

saw
- butthe nuclearchargeremainsthe
'Rleakv
- remainingelectronfeelsa

- hence,effectivenuclearcharge

\\.oet{\

- successiveionisationenergies

ih(neJtJ

coulombicattraction
to the nucleus
with each successiveremoval

removalof an electronfromquantumshell(n-l) requiresa higherenergythanthat

from shelln
ionisation
energiesincreasesin the orderof:
for the sameshelln, the successive
l <J<P<s

l8

chai/atomicstructurey'2004

l.E. kJmotl
590
1150
4540

eg:
Ca (g) -+ Ca- (g) + eCa* (g) -+ Ca2'19; + scat* (g) -+ ca3* (g) + e

DeducinEthe Electronic Gonfiquration from successive ionisation enercv data

. . exampleusingsuccessiveionisationenergiesfor a potassiumatom:

lg (1.E.
/ kJ mol'')

d"J.'

{lu
shltt

+lu

+o aecl&J,,

{h l,rh" +ha
en qn aqutnl

Number of electrons
ionised

Deductions
1 Thereare
. a large

quantumshells
in ionisation
energyis observedwhenelectrons
rv'vt'l/
ouantumshellcloserto the nucleus
are removed from an

to the removal
3 suchsharpincreasecan be seenfromthe plot,conesponding
the
18th
electron.
of the 2nd.1Oth
and

shell
2 Thiselectronis foundin the n = 'l
. it hasthe
L*.ti
ionisation
energy,
3 These8 electronsare in the n =

shell.

4 These8 electronsare in the n =

shell.

cl"wlt
5 Theseelectronsare
. these2 electronshavethe

eatieJf

to remove

to the nucleus,i.e.n =
shell
ionisationenergies
htlh.rr

of potassiumis ls "2r '+( b'3Pt +J'

Hence,the electronicconfiguration

I9

chai/atomicstrucrure/2004

':

Ex.1
The first eightsuccessiveionisationenergiesbran elementare as follows(in kJmol-l)
790

600

3200

4400 16100

19800

23800

Whichgroupin the PeriodicTabledoes this elementbelong?

O

laeg

v61

hrro +tn

ivocalr

a.n

n^

4 rtcalrrrc

x,E

twv*A

a..g

4r*^t

tt/

++1t 61+. gbcfon

rtn^. v'!C

rrk,

nn o, tba.a,tf oLtl ,

ry' .{ tlu e.io&aTarl. ,

Writedownitsouterelectronic
configuration.

23800

,r

funJ

ih
^uf

!a

l ^3 hP

Ex.2
Deducetheeleclronic
configuration
of the elementwithsuccessive
ionisation
energies
group
as shown.Hencedetermine
its
in the PerbdicTable.

ls E

No. of electronsremoved
llun

art

s
1^<r'lr't .sfiell

eltct.o6

ebcthh!

lr^

).

elcCfi.ort

lh

lh

tr= 3

stJ I

h t)

*oil"

E[ulrnrc <n/.1,r"ln t
I

Ef.rcrf I

,&.f, u

sfra,l'

a :l

lt" tsL2pc)E'

h-u? tr' .+ Teobc table,

20

chai,/atomicstructure/2004