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1
42He 12
6 C 0n
Characteristicsofthethreefundamentalparticlesare:
Macro Vision Academy, Burhanpur (M.P.)
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Electron
Symbol
Approximaterelativemass
Approximaterelativecharge
Massinkg
Massinamu
1/1836
-1
Proton
P
1
+1
Neutron
n
1
No charge
9.109 10 31
1.673 10 27
1.675 10 27
e or e
5.485 10 4
Actualcharge(coulomb) 1.602 10 19
Actual charge (e.s.u)
4.8 10 10
1.007
1.008
1.602 10 19
4.8 10 10
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iv) Somewereevenscatteredintheoppositedirectionatanangleof180[Rutherfordwasverymuch
surprisedbyitandremarkedthatItwasasincredibleasifyoufireda15inchshellatapieceoftissuepaper
anditcamebackandhityou].
Conclusions :
1.
Thefactthatmostofthe particlespassedstraightthroughthemetalfoilindicatesthemostpartoftheatom
isempty.
2.
Thefactthatfew particlesaredeflectedatlargeanglesindicatesthepresenceofaheavypositivelycharged
bodyi.e.,forsuchlargedeflectionstooccur -particlesmusthavecomeclosertoorcollidedwithamassive
positivelychargedbody,andhenameditnucleus.
3.
Atomic model:
i)
ii)
iii)
iv)
v)
Onthebasisoftheaboveobservation,andhavingrealizedthattherebounding -particleshadmetsomething
evenmoremassivethanthemselvesinsidethegoldatom,Rutherfordproposedanatomicmodelasfollows.
Alltheprotons(+vecharge)andtheneutrons(neutralcharge)i.e.nearlythetotalmassofanatomispresentin
averysmallregionatthecentreoftheatom.Theatomscentralcoreiscallednucleus.
Thesizeofthenucleus isverysmallincomparisonto thesizeoftheatom.Diameterofthenucleusisabout
1013 cmwhiletheatomhasadiameteroftheorder 108 cm.So,thesizeofatomis 105 timesmorethanthat
ofnucleus.(volumeofAtom=1015Nuclearvolume)
Mostofthespaceoutsidethenucleusisempty.
Theelectrons,equalinnumbertothenetnuclearpositivecharge,revolvearoundthenucleuswithhighspeedin
variouscircularorbits.
Thecentrifugalforcearisingduetothehighspeedofanelectronbalancesthecoulombicforceofattractionof
thenucleusandtheelectronremainsstableinitspath.Thusaccordingtohimatom consists of two parts (a)
nucleusand(b)extranuclearpart.Ifanalpha( )particleapproachesthetargetnucleusinsuchawaysuch
thatimpactparameteriszero,theitisdeflectedby1800,ThusKineticenergyof -particle=P.E.ofsystem
1
1
(Ze) (2e)
mv 2
2
4 0
rmin
rminisknownasdistanceofclosestapproach.
Defects of Rutherfords atomic model
1.
Position of electrons: Theexactpositionsoftheelectrons fromthenucleusarenotmentioned.
2.
Stability of the atom:NeilsBohrpointedoutthatRutherf ordsatomshouldbehighlyunstable.Accordingto
thelaw ofelectro-dynamics,theelectronshouldtherefore,continuouslyemitradiationandloseenergy.Asa
resultofthisamovingelectronwillcomecloserandclosertothenucleusandafterpassingthroughaspiralpath,
itshouldultimatelyfallintothenucleus.
Itwascalculatedthattheelectronshouldfallintothenucleusinlessthan 108 sec.Butitisknownthatelectrons
keepmovingoutsidedthenucleus.
TosolvethisproblemNeilsBohrproposedanimprovedformofRutherfordsatomicmodel.
BeforegoingintothedetailsofNeilsBohrmodelwewouldliketointroduceyousomeimportantatomicterms.
BOHRS ATOMIC MODEL
Bohrdevelopedamodelforhydrogenandhydrogenlikeone-electronspecies(hydrogenicspecies).Heapplied
quantumtheoryinconsideringtheenergyofanelectronbondtothenucleus.
Macro Vision Academy, Burhanpur (M.P.)
Atom)/260
Important postulates:Anatomconsistsofadensenucleussituatedatthecenterwiththeelectronrevolvingaround
itincircularorbitswithoutemittinganyenergy.Theforceofattractionbetweenthenucleusandanelectronis
equaltothecentrifugalforceofthemovingelectron.
Ofthefinitenumberofcircularorbitspossiblearoundthenucleus,andelectroncanrevolveonlyinthoseorbits
whoseangularmomentum(mvr)isanintegralmultipleoffactorh/ 2 .
mvr
nh
2
where,m=massofthe electron
v=velocityoftheelectron
n=orbitnumberinwhichelectronispresent
r=radiusoftheorbit
Aslongasanelectronisrevolvinginanorbititneitherlosesnorgainsenergy.Hencetheseorbitsarecalled
stationarystates.Eachstationarystateisassociatedwithadefiniteamountofenergyanditisalso knownas
energylevels.Thegreaterthedistanceoftheenergylevelfromthenucleus,themoreistheenergyassociated
withit. Thedifferentenergylevelsarenumberedas 1,2,3,4,(fromnucleusonwards)orK,L,M,Netc.
Ordinarilyanelectroncontinuestomoveinaparticularstationarystatewithoutlosingenergy.Such astable
stateoftheatomiscalledasgroundstateornormalstate.
Ifenergyissuppliedtoanelectron,itmayjump(excite)instantaneouslyfromlower energy(say1)tohigher
energy level(say 2, 3, 4,etc) by absorbing onequantum ofenergy. Thisnew state ofelectronis called as
excited state. The quantum ofenergy absorbed is equal to the difference in energies ofthe two concerned
levels.
Sincetheexcitedstateislessstable,atomwillloseitsenergyandcomebacktothegroundstate.
Energyabsorbedorreleasedinanelectronjump, ( E) isgivenby
E E2 E1 h
Where E2 and E1 aretheenergiesoftheelectroninthefirstandsecondenergylevels,and isthefrequency
ofradiationabsorbedoremitted.
Note:If the energy supplied to hydrogen atom is less than 13.6 eV, it will accept or absorb only those quanta
which can take it to a certain higher energy level i.e., all those photons having energy less than or more
than a particular energy level will not be absorbed by hydrogen atom. But if energy supplied to hydrogen
atom is more than 13.6 eV then all photons are absorbed and excess energy appear as kinetic energy of
emitted photo electron.
Merits of Bohrs theory
i)Theexperimentalvalueofradiiandenergiesinhydrogenatomareingoodagreementwiththat
calculatedonthebasisofBohrstheory.
ii)Bohrsconceptofstationarystateofelectronexplainstheemissionandabsorptionspectraof hydrogenlike
atoms.
iii)Theexperimentalvaluesofthespectrallinesofthehydrogenspectrumareincloseagreement with the
calculatedbyBohrstheory
Limitations of Bohrs Theory
i)Itdoesnotexplainthespectraofatomsorionshavingmorethanoneelectron.
ii) Bohrs atomicmodel failed to account for theeffect ofmagnetic field (Zeeman effect)orelectric field
(Starkeffect)onthespectraofatomsorions.Itwasobservedthatwhenthesourceofaspectrumisplacedin
Atom)/260
astrongmagneticorelectricfield,eachspectrallinefurthersplitsintoanumberoflines.Thisobservationcould
notbeexplainedonthebasisofBohrsmodel.
iii)de-Brogliesuggestedthatelectronslikelighthavedualcharacter.Ithasparticleandwave
character.Bohrtreatedtheelectrononlyas particle.
iv)AnotherobjectiontoBohrstheorycamefromHeisenbergsUncertaintyPrinciple.Accordingtothisprinciple
itisimpossibletodeterminesimultaneouslytheexactpositionandmomentumofasmallmovingparticlelikean
electron.ThepostulateofBohr,thatelectronsrevolveinwell
definedorbitsaroundthenucleuswithwelldefinedvelocitiesisthusnotattainable
Bohrs Calculation
i)
Radius and Energy levels of hydrogen atom: Consider an electron of mass m and charge e revolving
arounda nucleusofchargeZe(where,Z=atomicnumberandeisthechargeofthe
proton) with a
tangentialvelocityv.ristheradiusoftheorbitinwhichelectronisrevolving.
ByCoulombsLaw,theelectrostaticforceofattractionbetweenthemovingelectronandnucleus
i s
Coulombicforce
K
KZe2
r2
1
40 (where 0 ispermitivityoffreespace)
K 9 109 Nm2C 2
InC.G.S.units,valueofK=1dyne cm 2 (esu)2
mv 2
r
Sincetheelectrostaticforcebalance thecentrifugalforce,forthestableelectronorbit.
Thecentrifugalforceactingontheelectronis
mv 2 KZe2
2
r
r
(i)
KZe 2
(ii)
mr
AccordingtoBohrspostulateofangularmomentum quantization,wehave
2
(or) v
mvr
v
nh
2
nh
2mr
n2h2
4 2m 2r 2
Equating(2)and(3)
v2
(iii)
KZe2
n2h2
2 2 2
mr
4 m r
Solvingforrweget r
n2h2
4 2mKZe 2
wheren=1,2,3,
Henceonlycertainorbitswhoseradiiaregivenbytheaboveequationareavailablefortheelectron.
Thegreaterthevalueofn,i.e.,fartherthelevelfromthenucleusthegreateristheradius.
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Theradiusofthesmallestorbit(n=1)forhydrogenatom(Z=1)is r0 .
r0
n2h 2
12 (6.626 1034 )2
5.29 10 11m
2
2
2
31
19 2
9
4 me K 4 (3.14) 9 10 (1.6 10 ) 9 10
r0 0.529
RadiusofnthorbitforanatomwithatomicnumberZissimplywrittenas
n2
n2
0.529
z
z
Illustration 1 : Calculate the ratio of the radius of Be3+ ion in 3rd energy level to that of He+
ion in2nd energy lev el.
rn r0
Solution:
n2
z
2
r1 n1 z2
r2 n2 z1
n1 3 ; n2 2 ;
z1 4
(for Be3+ )
z2 2
(for He )
2
ii)
r1 3 2 9
r2 2 4 8
Energy level of Hydrogen atom: Thetotalenergy,Eoftheelectronisthesumofkineticenergy
andpotentialenergy.Kineticenergyoftheelectron= 12 mv 2
Potentialenergy
KZe2
r
KZe2
r
Fromequation(1)weknowthat
Totalenergy
2
2 mv
(4)
mv 2 KZe2
2
r
r
1
KZe2
mv 2
2
2r
Substitutingthisinequation(4)
Totalenergy(e)
KZe2 KZe2
KZe2
2r
r
2r
1
KE PE, KE TE
2
Substitutingforr,givesus
2 2mZ2e 4K 2
wheren=1,2,3,
n2h 2
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This expression shows that only certain energies are allowed to the electron. Since this energy expression
consistssomanyfundamentalconstant,wearegivingyouthefollowingsimplifiedexpressions.
E 21.8 1012
En 13.6
Z2
Z2
Z2
19
erg
21.8
10
13.6
peratom
Jperatom=
eVperatom
n2
n2
n2
z2
eVper atom
n2
Z2
kcal/mole(1cal=4.18J)
n2
Theenergiesarenegativesincetheenergyoftheelectronintheatomislessthantheenergyofafreeelectron
(i.e.,theelectronisatinfinitedistancefromthenucleus),whichistakenaszero.Thelowestenergylevelofthe
atomcorrespondston=1,andasthequantumnumberincreases,Ebecomelessnegative.
Whenn= ,E=0whichcorrespondstoanionizedatomi.e.,theelectronandnucleusareinfinitelyseparated.
H H e (ionization).
Illustration 2 : How far from the nucleus is the electron in a hydrogen atom if it has energy
0.850 eV.
Solution:
En
Z2
21.69 1019
2
n
Z2
21.69 10 19 0.85 1.6 1019
n2
n=4(Z=1)
iii)
of
n2
16
0.529
0.529 8.46
Z
1
Velocity of electron
nh
nh
;v
2
2 mr
Bysubstitutingforrwearegetting
Weknowthat, mvr
2 KZe2
nh
8
Whereexceptingnandzallareconstant,v= 2.18 10
Z
cm / sec.
n
FurtherapplicationofBohrsworkwasmade,tootheroneelectronspecies(Hydrogenicion)
iv)
such as He
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Duringeachjumps,energyisemittedintheformofaphotonoflightofdefinitewavelengthorfrequency.The
frequency ofthe photon oflight thus emitted depends upon the energy difference of the two energy levels
concerned( n1, n2 )andis givenby
h E2 E1
2 2mZ e 4K 2
h2
1
1
2 2
n1 n 2
2 2mZ2 e 4K 2 1
1
2 2
3
h
n1 n2
Thefrequenciesofthespectrallinescalculatedwiththehelpofaboveequationarefoundtobein g o o d
agreementwiththeexperimentalvalues.Thus,Bohrstheoryelegantlyexplainsthelinespectrumofhydrogen
andhydrogenicspecies.
BohrhadcalculatedRydbergconstantfromtheaboveequation.
C 2 2mZ2e 4K 2 1
1
2 2
3
h
n1 n2
1
22mZ2 e 4K 2
h3c
where
1
1
2 2
n1 n2
2 2me 4K 2
1.097 10 7 m 1 or 109678 cm1
h3 c
i.e.Rydbergconstant(R)
1
RZ 2
1
1
2 2
n1 n2
wavenumber..
Illustration 3 : Find the wavelengths of the first line of He+ ion spectral series whose interval
1
1
4
1
between extreme lines is 2.7451 10 cm
1
2
Solution:
Extremelinesmeansfirstandlast.
1
1
RZ2
1 2
1
1
2
2 2 RZ
n
2.7451 104
109677.76 22
(n1 1)2
1
1
RZ 2
2
(n1 1)2
n1 (n1 1)
(n1 1) 4
n1 3
Wavelengthoffirstline,
1
1
1
109677.76 22 2 2
4
3
4689 10 8 cm 4689
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Electromagnetic Energy
NewtonwasfirstpersontocommentonthenatureoflightintermsofCorpusculartheoryofLight.According
tothis theorylight is a streamofparticlescommonly knownas corpusclesoflight. He wasable toexplain
reflectionandrefraction,themostcommonphenomenonoflight.Buttheotherphenomenonlikediffractionand
interferencecouldnotbeexplainedonthebasisofthistheory.
Maxwell, in 1956 proposed that radiant energy (light) has wave characteristics. Light according to him is
Electromagnetic Wave arising due to the disturbance created by electric and magnetic fields oscillating
perpendiculartoeachotherinspace.Likeallothermechanicalwaves,itischaracterisedbyvelocityc,frequency
,wavelength whicharerelatedas:
c .Thevalueofcisconstantandequalto 3 108 m / s.
Electromagnetic Spectrum
Electromagneticwaveorradiationisnotasinglewavelengthradiation,butamixtureofvariouswavelengthor
frequencies.Allthefrequencieshavesamespeed.
Ifall thecomponentsofElectromagnetic Radiation(EMR)arearranged inorderofdecreasing orincreasing
wavelengthsorfrequencies,thepatternobtainedisknownasElectromagneticSpectrum.Thefollowingtable
showsallthecomponentsoflight.
S.No. Name
Wavelength (nm)Frequency (Hz)
Source
1.
Radiowave 3 1014 3 10 7
Alternatingcurrentofhigh frequency
1 10 5 1 10 9
2.
Microwave 3 10 7 6 10 6
3.
4.
Visible
5.
Ultraviolet(UV)3800-150
6.
X-Rays
150-0.1
2 1016
7.
rays
0.1-0.01
3 1019 3 1020
Secondary effectofradioactivedecay
8.
CosmicRays
0.01-zero
3 1020 -infinity
Outer space
7600 3800
1 10 9 5 1011
Klystrontube
Continuous Spectrum: When sunlight (white light) is passed through a prism, it is dispersed orresolved into a
continuousspectraofcolours.ItextendsfromRED(7600)atoneendtotheVIOLET(3800)atotherend.
In this region,all the intermediate frequencies between redand violet are present. The typeofspectrum is
knownasContinuousSpectrum.,Hencecontinuousspectraisonewhichcontainsradiationofallthefrequencies.
Discontinuous Spectrum: Lightemittedfromatomsheatedinaflameorexcitedelectricallyingasdischargetube,
doesnotcontainacontinuousspectrumofwavelengths(orfrequencies).Itcontainsonly certainwell-defined
wavelength(or frequencies).The spectrumpattern appearsasa seriesofbrightlines (separatedby gapsof
darkness)andhence calledasLine-Spectrum.
One notable featureobserved is, that each elementemits a characteristic spectrum, suggestingthat there is
discreterelationbetweenthespectrumcharacteristicsandtheinternalatomicstructureofanatom.
QUANTUM MECHANICAL MODEL OF ATOM
Theatomicmodelwhichisbasedontheparticleandwavenatureoftheelectronisknownaswaveorquantum
mechanicalmodeloftheatom.ThiswasdevelopedbySchrodingerin1926.Thismodeldescribestheelectron
asathreedimensionalwaveintheelectronicfieldofpositivelychargednucleus.Schrodingerderivedanequation
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whichdescribeswavemotionofpositivelychargednucleus.Schrodingerderivedanequationwhichdescribes
wavemotionofanelectron.Thedifferentialequationis
d2 d2 d2 8 2m
2 (E V) 0
dx2 dy 2 dz2
h
wherex,y,zarecertaincoordinatesoftheelectron,m=massoftheelectron,E=totalenergyoftheelectron.
V=potentialenergyoftheelectron;h=Plancksconstantand (psi)=wavefunctionofthe electron.
Significance of : Thewavefunctionmayberegardedastheamplitudefunctionexpressedintermsofcoordinates
x,yandz.Thewavefunctionmayhavepositiveornegativevaluesdependinguponthevalueofcoordinates.
ThemainaimofSchrodingerequationistogivesolutionforprobabilityapproach.Whentheequationissolved,
itisobservedthatforsomeregions ofspacethevalueof isnegative.Butthe probabilitymustbealways
positiveandcannotbenegative,itisthus,propertouse 2 infavourof .
Significance of 2 : 2 isaprobabilityfactor.Itdescribestheprobabilityoffindinganelectronwithinasmallspace.
Thespaceinwhichthereismaximumprobabilityoffindinganelectronistermedasorbital.Theimportantpoint
ofthesolutionofthewaveequationisthatitprovidesasetofnumberscalledquantumnumberswhichdescribe
energiesoftheelectroninatoms,informationabouttheshapesandorientationsofthemostprobabledistribution
ofelectronsaroundnucleus.
HEISENBERGS UNCERTAINTY PRINCIPLE
Allmoving objectsthat wesee arounduse.g., acar,aball thrownin the airetc,movealong definitepaths.
Hencetheirpositionandvelocitycanbemeasuredaccuratelyatanyinstantoftime.Isitpossibleforsubatomic
particlealso?
As a consequence ofdual nature ofmatter. Heisenberg,in 1927 gave a principle about the uncertainties in
simultaneousmeasurementofpositionandmomentum(mass velocity)ofsmallparticles.Thisprinciplestates.
Itisimpossibletomeasuresimultaneouslythepositionandmomentumofasmallmicroscopicmovingparticle
withabsoluteaccuracyorcertaintyi.e.,ifanattemptismadetomeasureanyoneofthesetwoquantitieswith
higheraccuracy,theotherbecomeslessaccurate.
Theproductoftheuncertaintyinposition( x) andtheuncertaintyinthemomentum (p m. v wheremis
themassoftheparticleand v istheuncertaintyinvelocity)isequaltoorgreaterthan h / 4 wherehisthe
Plancks constant.
Thus,themathematicalexpressionfortheHeisenbergsuncertaintyprincipleissimplywrittenas
h
4
Explanation of Heisenbergs uncertainty Principle: Supposeweattempttomeasureboththepositionandmomentum
ofanelectron,topinpointthepositionoftheelectronwehavetouselightsothatthephotonoflightstrikesthe
electronandthereflectedphotonisseeninthemicroscope.Asaresultofthehitting,thepositionaswellasthe
velocityoftheelectronis distributed.Theaccuracywithwhichthepositionofthe particlecanbe measured
dependsuponthewavelengthofthelightused.Theuncertaintyinpositionis+ .Theshorterthewavelength,
thegreateristheaccuracy.Butshorterwavelengthmeanshigherfrequencyandhencehigherenergy.Thishigh
energyphotononstrikingtheelectronchangesitsspeedaswellasdirection.Butthisisnottrueformacroscopic
movingparticle.HenceHeisenbergsuncertaintyprincipleisnotapplicabletomacroscopicparticles.
Illustration 4 : The uncertainty for the calculation of radius of the 1st Bohr orbit is 2% for the hydrogen
atom. What will be the uncertainty in velocity of electron in the 1st Bohr orbit. (h = 6.626
1034 Joule.sec, me = 9.1 1031 kg)
x.p h / 4 or E t
10
Atom)/260
Solution:
h
4
6.626 1034
4 3.14 9.1 1031 1.06 1012
v 5.47107m/sec.
ATOMIC SPECTRUM
If the atom gains energy the electron passes from a lower energy level to a higher energy level, energy is
absorbedthatmeansaspecificwavelengthisabsorbed.Consequently,adarklinewillappearinthespectrum.
Thisdarklineconstitutestheabsorption spectrum.
Hydrogen spectrum: Ifanelectricdischarge ispassedthroughhydrogengastakenin adischargetubeunder
lowpressure,andtheemittedradiationisanalysedwiththehelpofspectrograph,itisfoundtoconsistofaseries
ofsharp lines in the UV, visible and IR regions. This series oflines is known as line oratomic spectrum of
hydrogen.Thelinesinthevisibleregioncanbedirectlyseenonthephotographicfilm.
Eachlineofthespectrumcorrespondstoalightofdefinitewavelength.Theentirespectrumconsistsofsixseries
oflineseachseries,knownaftertheirdiscovererastheBalmer,Paschen,Lyman,Brackett,PfundandHumphrey
series.Thewavelengthofalltheseseriescanbeexpressedbyasingle formula.
1
1
1
R 2 2
n1 n 2
=wave number
=wave length
R=Rydbergconstant(109678 cm 1 )(R=1.097 107 m1)
n1 and n2 haveintegralvaluesasfollows
n1
n2
Series
Main spectral lines
Lyman
1
2,3,4etc
Ultra-violet
Balmer
2
3,4,5etc
Visible
Paschen
3
4,5,6etc
Infra-red
Brackett
4
5,6,7etc
Infra-red
Pfund
5
6,7,8etc
Infra red
Note:AlllinesinthevisibleregionareofBalmerseriesbutreverseisnottrue,i.e.,allBalmerlines
will
notfallinvisibleregion
Thepatternoflinesinatomicspectrumischaracteristicofhydrogen.
Types of emission spectra
i)
Continuous spectra: Whenwhitelightfrom anysourcesuchassunorbulbis analysedbypassingthrougha
prism,itsplitsupintosevendifferentwidebandsofcolourfromviolettored(likerainbow).Thesecolouralso
continuousthateachofthemmergesintothenext.Hencethespectrumiscalledascontinuousspectrum.
ii)
Line spectra:Whenanelectricdischargeispassedthroughagasatlowpressurelightisemitted.Ifthislightis
resolved byaspectroscope,itisfoundthatsomeisolatedcolouredlinesareobtainedonaphotographicplate
11
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separatedfromeachotherbydarkspaces.Thisspectrumiscalledlinespectrum.Eachlineinthe spectrum
correspondstoaparticularwavelength.Eachelement givesitsowncharacteristicspectrum.
PHOTOELECTRIC EFFECT
It was observed by Hertz and Lenard around 1880 that when a clean metallic surface is irradiated by
monochromaticlightofproperfrequency,electronsareemittedfrom it.Thisphenomenon ofejectionofthe
electronsfrommetalsurfacewascalled asPhotoelectricEffect.
Itwasobservedthatifthefrequencyofincidentradiationisbelowacertainminimumvalue(thresholdfrequency),
noemissiontakesplacehoweverhightheintensityoflightmaybe.
Anotherimportantfeatureobservedwasthatthekineticenergyoftheelectronsemittedisindependentofthe
Intensityofthelight.Thekineticenergyoftheelectronsincreaseslinearlywiththefrequencyofincidentlight
radiation.ThiswashighlycontrarytothelawsofPhysicsatthattimei.e.theenergyoftheelectronsshould
havebeenproportionaltotheintensityofthelight,notonthefrequency.
These features could not be properly explained on the basis of Maxwells concept of light i.e. light as
electromagnetic wave.
In 1905, Einstein applied Plancks quantum theory oflight to account for the extraordinary features ofthe
photoelectriceffect.Heintroducedanewconceptthatlightshowsdualnature.Inphenomenonlikereflection,
refractionanddiffractionitshowswavenatureandinphenomenonlikephotoelectriceffects,itshowsparticle
nature.Accordingtotheparticlenature,theenergyofthelightiscarriedindiscreteunitswhosemagnitudeis
proportionaltothefrequencyofthelightwave.Theseunitswerecalled asphotons(orquanta).
AccordingtoEinstein,whena quantumoflight(photon)strikesametalsurface,it impartsitsenergytothe
electronsinthemetal.Inorderforanelectrontoescapefromthesurfaceofthemetal,itmustovercomesthe
attractiveforce ofthe positive ionsinthe metal.So a partofthephotonsenergy isabsorbedby themetal
surfacetoreleasetheelectron,thisisknownasworkfunctionofthesurfaceandisdenotedby .Theremaining
partoftheenergyofthephotongoesintothekineticenergyoftheelectronemitted.IfEistheenergyofthe
photon,KEisthekineticenergyoftheelectronand betheworkfunctionofthemetalthenwehave;
h0 and Ei h
KE Ei
KE h h 0 h( 0 )
Also,ifmbethemassandvbethevelocityoftheelectronejectedthen
KE
mv 2 h( 0 ) .
Note:The electromagnetic Radiation (or wave) now emerges as an entity which shows dual nature i.e.,
sometimes as Wave and sometimes as Particle (quantum aspect).
Illustration 5 :
In a photoelectric experiment, the collector plate is at 2.0 V with respect to emitter
plate made of copper (work function 4.5 eV). The emitter is illuminated by a source of
mono-chromatic light of wavelength 200 nm. Find the minimum and maximum kinetic
energy of photoelectrons reaching the collector.
Solution:
Sinceplatepotentials2V,minimumK.E.willbe2eV.Formax.K.E.usethefollowing
relation:
Absorbedenergy=Thresholdenergy+K.E.
hc
4.5 1.6 10 19 K.E.
12
Atom)/260
Theaboveequationisapplicabletomaterialparticleifthemassandvelocityofphotonisreplacedbythemass
andvelocityofmaterialparticle.Thusforanymaterialparticlelikeelectron.
But c /
h / mv (or)
h
p
wheremv=pisthemomentumofthe particle.
Illustration 6 :
13.6 eV is needed for ionization of a hydrogen atom. An electron in a hydrogen atom in
its ground state absorbs 1.50 times as much energy as the minimum required for it to
escape from the atom. What is the wavelength of the emitted electr on? ( me = 9.109 10
31
kg, e = 1.602 1019 coulomb, h = 6.63 1034 J.s)
Solution: 1.5timesof13.6eVi.e.,20.4eVisabsorbedbythehydrogenatomoutofwhich6.8eV
(20.413.6)isconvertedtokineticenergy.KE=6.8eV=6.8(1.602 1019 coulomb)
(1volt)=1.09 1018 J.
Macro Vision Academy, Burhanpur (M.P.)
13
Atom)/260
Now, KE
or, v 2
Illustration 7 :
1
mv 2
2
KE
2(1.09 10 18 J)
1.55 106 m / s
(9.109 10 31kg)
h
(6.63 10 34 J.s)
4.70 10 10 metres
Show that de-Broglie wavelength of electrons accelerated V volt is very
1/2
150
nearly given by (in ) =
V
Solution:
h
2e Vm
h2
1020
2e Vm
1/2
1/2
150
1/2
QUANTUM NUMBERS
TounderstandtheconceptofQuantumNumbers,wemustknowthemeaningofsometermsclearlysoasto
avoidanyconfusion.
Energy Level: Thenon-radiatingenergy circularpathsaroundthenucleusarecalledasEnergyLevelsorShells.
Thesearespecifiedbynumbershavingvalues1,2,3,4,...orK,L,M,N,...inorderofincreasingenergies.
Theenergyofaparticularenergylevelisfixed.
Sub-Energy Level: Thephenomenonofsplittingofspectrallinesinelectricandmagneticfieldsrevealsthatthere
mustbeextraenergylevelswithinadefiniteenergylevel.ThesewerecalledasSub-EnergyLevelsorSubShells.Therearefourtypesofsub-shellsnamely;s, p, d, f.
Firstenergylevel(Kor)hasonesub-shelldesignatedas1s,thesecondenergylevel(Lor2)has twosubshellas2s&2p,thethirdenergylevel(Mor3)hasthreesubshellas3s,3pand3d,andthefourthenergylevel
(Nor4)hasfoursub-shellsas4s,4p,4dand4f.Theenergyofsub-shellincreasesroughlyintheorder:s<p
<d<f.
Orbital: Each sub-energy level (sub-shell)is composed ofone ormore orbitals. These orbitals belonging to a
particularsub-shellhave equalenergiesandarecalledasdegenerateorbitals.s-sub-shellhasoneorbital,p
hasthreeorbitals,dhavefiveorbitalsandfhassevenorbitals.
Todescribe ortocharacterize theelectronsaround thenucleusinan atom,aset offournumbers isused,
calledasQuantumNumbers.Thesearespecifiedsuchthatthestatesavailabletotheelectronsshouldfollows
thelaws ofquantum mechanicsorwavemechanics.
Principal Quantum Number: (n): This quantum number represents the main energy levels (principal energy
levels)designatedasn=1,2,3,...orthecorrespondingshellsarenamedasK,L,M,N,...respectively.It
givesanideaofpositionandenergyofanelectron.Theenergyleveln=1correspondstominimumenergy
andsubsequentlyn=2,3,4,...,arearrangedinorderofincreasingenergy.
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Higheristhevalueofn,greaterisitsdistancefromthenucleus,greaterisitssizeandalsogreaterisitsenergy.
Italsogivesthetotalelectronsthatmaybeaccommodatedineachshell,thecapacityofeachshellisgivenbythe
formula 2n2 ,wheren:principalquantumnumber..
Azimuthal Quantum Number ( ):Thisnumberdeterminestheenergyassociatedwiththeangularmomentumofthe
electron about the nucleus. It is also called as the angular momentum quantum number. It accounts for the
appearanceofgroupsofcloselypackedspectrallinesinelectricfield.
Itcanassumeallintegralvaluesfrom0ton1.Thepossiblevaluesof are:0,1,2,3,...,n1.
Eachvalueof describesaparticularsub-shellinthemainenergylevelanddeterminestheshapeoftheelectron
cloud.
Whenn=1, =0,i.e.,itsenergylevelcontainsonesub-shellwhichiscalledasas-sub-shell.Sofor =0,the
correspondingsub-shellisas-sub-shell.Similarlywhen =1,2,3,thesub-shellsarecalledp, d, fsub-shells
respectively.
Asyouknowforn=1, =0,thereisonlyonesub-shell.Itisrepresentedby1s.Nowforn=2,lcantaketwovalues(the
totalnumberofvaluestakenby isequaltothevalueofninaparticularenergylevel).Thepossiblevaluesof are0,1.
Thetwosub-shellrepresentingtheIIndenergylevelare2s,2p.Inthesamemanner,forn=3,threesub-shellsaredesignated
as3s,3p,3dcorrespondingto =0,1,2,andforn=4,foursub-shellsaredesignatedas4s,4p,4d,4fcorrespondingto
=0,1,2,3.
TheorbitalAngularmomentumofelectron= ( 1)
h
.
2
Notethatitsvaluedoesnotdependuponvalueofn.
Magnetic Quantum Number (m):Anelectronwithangularmomentumcanbethoughtasanelectriccurrentcirculating
inaloop.Amagneticfieldduetothiscurrentisobserved.Thisinducedmagnetismisdeterminedbythemagnetic
quantumnumber.Undertheinfluenceofmagneticfield,theelectronsinagivensub-energylevelprefertoorient
themselvesincertainspecificregionsinspacearoundthenucleus.Thenumberofpossibleorientationsforasubenergylevelisdeterminedbypossiblevaluesofmcorrespondstothenumberoforbitalsinagivensub-energy
level).
mcanhaveanyintegralvaluesbetween to+ including0,i.e.,m= ,0+, .Wecansaythatatotalof
(2 +1)valuesofmarethereforagivenvalueof .
Inssub-shellthereisonlyoneorbital[ =0,m=(2 +1)=1].
Inpsub-shelltherearethreeorbitalscorrespondingtothreevaluesofm:1,0+1.[ =1
m=(2 +1)=3].Thesethreeorbitalsarerepresentedas p x , p y , p z alongX,Y,Zaxesperpendiculartoeach
other.
Indsub-shell,therearefiveorbitalscorrespondingto2,1,0+1,+2,
[ =2 m=( 2 2 1) 5] .Thesefiveorbitals arerepresentedas d xy ,dyz ,dzx ,d x2 y 2 ,d z2 .
Infsub-shelltherearesevenorbitalscorrespondingto3,2,1,0,+1,+2,+3
[ =3 m= (2 3 1) 7] .
Spin quantum Number (s): When an electron rotates around a nucleus it also spins about its axis. Ifthe spin is
clockwise,itsspinquantumnumberis+1/2andisrepresentedas .Ifthespinisanti-clockwise,itsvalueis1/
2andisrepresentedas .Ifthevalueofsis+1/2,thenbyconvention,wetakethatelectronasthefirstelectron
inthatorbitalandifthevalueofsis1/2,itistakenassecondelectron.
Illustration 8 :
Solution:
Write down the values of quantum numbers of all the electrons present in the outermost
orbit of neon (At. No. 10)
Theelectronicconfigurationofneonis1s 2,2s2,2p6.Valuesofquantumnumbersare:
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+1/2,-1/2
2p x 2
+1/2,-1/2
2py 2
+1/2,-1/2
2p z 2
+1/2,-1/2
2s
Illustration 9 : a) An electron is in 6f-orbital. What possible values of quantum numbers n, , m and s can
it have?
b) What designation is given to an orbital having (i) n = 2, =1, and (ii) n = 3, = 0?
Solution:
a)Foranelectronin6f-orbital,quantumnumberare:
n=6, =0,1,2,3,4,5=0,m=0, =1,m=1,0,+1, =2,m=2,1,0,+1,
+2, =3,m=3,2,1,0,+1,+2,+3, =4,m=4,to+4
including0, =5,m=-5to+5includingzero.
b)(i)2p,(ii)3s
AUFBAU PRINCIPLE
AufbauisaGermanwordmeaningbuildingup.Thisgivesusasequenceinwhichvarioussub-shellsarefilled
updependingontherelativeorderoftheenergyofthesubs-shells.Thesub-shellwithminimumenergyisfilled
upfirstandwhenthisobtainsmaximumquotaofelectrons,thenthenextsubshellofhigherenergystartsfilling.
1s
2s
2p
3s
3p
3d
4s
4p
4d
5s
5p
5d
6s
6p
4f
7s
1s,2s,2p,3s,3p,4s,3d,4p,5s,4d,5p,6s,4f,5d,6p,7s,5f,6d,7p
Sub-Shell
n
n
1s
2s
2p
2
2
0
1
2
3
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Lowestvalueofn
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3s
3p
4s
3d
4p
3
4
2
1
5
5
5s
4d
5p
4
5
2
1
6
6
6s
4f
5d
4
5
3
2
7
7
6p
7s
5f
6d
5
6
3
2
8
8
7p
Lowestvalueofn
Lowestvalueofn
Lowestvalueofn
Lowestvalueofn
Lowestvalueofn
(right)
(right)
Similarlythefollowingelementshaveslightlydifferentconfigurationsthanexpected.
Nb [Kr] 4d4 5s1
Mo [Kr] 4d4 5s1
Ru [Kr] 4d7 5s1
Rh [Kr] 4d8 5s1
Pd [Kr] 4d10 5s0
Ag [Kr] 4d10 5s1
Pt [Xe] 4f 14 5d9 6s1
Au [Xe] 4f 14 5d10 6s1
SHAPES OF ATOMIC ORBITALS
i)
s-orbital: Anelectronisconsideredtobeimmersed outintheform ofacloud.Theshapeofthecloudisthe
shapeoftheorbital.Thecloudisnotuniformbutdenserintheregionwheretheprobabilityoffindingtheelectron
ismaximum.
Theorbitalwiththelowestenergyisthe1sorbital.Itisaspherewithitscenterofthenucleusoftheatom.The
s-orbitalissaidtosphericallysymmetricalaboutthenucleus,sothattheelectronicchargeisnotconcentratedin
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anyparticulardirection.2sorbitalisalsosphericallysymmetricalaboutthenucleus,butitislargerthan(i.e.,
awayfrom)the1s orbit.
y
2s
1s
nucl eus
radial node
ii)
z
y
px
iii)
py
pz
d-orbitals:Therearefived-orbitals.Theshapesoffourd-orbitalsresemblefourleafcloves.Thefifthd-orbital
looksdifferent.Theshapesoftheseorbitalsaregivenbelow.
y
x
d xy
dyz
d x 2 y 2
dzx
dz 2
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KEY CONCEPTS
1.
AccordingtoDaltonsatomictheoryatomisconsideredassmallestindivisibleparcticleofmatter.
Electron,protonandneutronarethesubatomicparticles.
2.
According to Rutherford model atom consist ofnucleus. The positive charge and the mass of the atom is
concentratedinthenucleus.Theelectronsrevolveroundthenucleusincircularpaths.
3.
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4.
5.
Energyofonequantum=h
AccordingtoBohrstheoryelectronrevolveroundthenucleusonlyinthoseorbitwhereitsangularmomentum
isanintegralmultipleof
h
.
2
h
and E h
2
6.
mvr n
7.
ImportantformulationderivedfromBohrsatomicmodel.
n2h2
n2 0
0.529
A
4 2 mkZe 2
Z
(i)
Radius(r)=
(ii)
Energy(E)ofelectroninnthorbit=
2 2 mZ 2e 4 K 2
Z2
13.6
eV
n 2h 2
n2
Energy(E)ofelectroninnthorbit= 2.18 10
8
18
z2
J / atom
n2
Z
cm / sec.
n
(iii)
Velocityofelectroninnthorbit(v)= 2.18 10
(iv)
Numberofrevolutionspersecondbyanelectroninnthorbit=
V
2 r
Z 2 me 4
(v)
Numberofrevolutionspersecondbyanelectroninnthorbit=
(vi)
Frequencyofelectroninthenthorbit= 6.62 10
15
Z2
n3
8.
BohrstheoryofatomisapplicabletoonlyHydrogenlikespecies
9.
1
1
1
RH Z2 2 2 ; RH =Rydbergsconstant
n1 n2
10.
11.
2 20 n3 h3
h
h
p mV
h
WhereEisKEoftheparcticle
2 Em
12.
AccordingtoHeisenbergsuncertainityprinciple x.p
13.
Principalquantumnumber(n)=1,2,3,
14.
Azimuthalquantumnumber( )=0,1,2 n 1
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h
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15.
Magneticquantumnumber m to
16.
Spinquantumnumber(s)
17.
Orbitalangularmomentum 1
18.
19.
20.
21.
22.
Numberofsubshellinashell=n
Numberofmaximumorbitalsinashell= n 2
Numberofmaximumorbitalsinasubshell= 2 1
Noofradialnodes n 1
Noofangularnodes=
1
1
and
2
2
h
1h
2
1
Z2
1
1
Z2 ; He 2H
He 9.12 22.8nm
Hence,
H
ZHe 4
4
36.
( probabilityoffindinganelectroniszeroatnode)
1 1 1
0
4 2 a0
37.
3/ 2
r0
r0
r0
r / a
; 2a 0 r0
2
e 0 0 2 0; 2
a0
a0
a0
h
6.627 10 34
mu
0.1 100
Or
6.627 10 35 m 6.627 10 25
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