TheAtomicTheoryand

Electronic Structure
ElectronicStructure
AVisualHistoricalApproach

Part 1
Part1
DavidA.Katz
DepartmentofChemistry
D
f Ch i
PimaCommunityCollege
Tucson,AZU.S.A.
Voice:5202066044Email:dkatz@pima.edu
Website:http://www.chymist.com

TheoriesofMatter
TheGreeksandHindusappeartohavedeveloped
theoriesonmatter.
MostofthewritingsareattributedtotheGreeksdueto
theamountofrecordedinformationthathassurvivedto
th
thepresent.
t
Greeksthoughtsubstancescouldbeconvertedor
transformedintootherforms.
Theyobservedthechangingofstatesduetoheatand
equateditwithbiologicalprocesses.
TheGreekswerephilosophersandthinkers,not
experimentalists,sotheydidnotconductexperimentsto
y
verifytheirideas.

 ThalesofMiletus(about624about527B.C.)
Proposedthatwateristheprimalmatterfromwhich
everythingoriginated.
Heisalsocreditedwithdefiningasoul
g
asthatwhich
possesseseternalmotion.

Anaximander(610546B.C.)
The
Theprimarysubstance,theapeiron,
primary substance the apeiron waseternaland
was eternal and
unlimitedinextension.Itwasnotcomposedofanyknown
elementsanditpossessedeternalmotion(i.e.,asoul).

Anaximenes(585524B.C.)
Anaximenes (585 524 B C )
Statedthatairistheprimarysubstance
Suggesteditcouldbetransformedintoothersubstances
bythinning(fire)orthickening(wind,clouds,rain,hail,
earth,rock).

 HeraclitusofEphesus(544484B.C.)
ffire istheprimevalsubstance
p
Changeistheonlyreality.

ThePythagoreans(Pythagoras(570490B.C.))
R
Reducedthetheoryofmattertoamathematicaland
d d h h
f
h
i l d
geometricbasisbyusinggeometricsolidstorepresentthe
basicelements:

cube=earth
cube
earth
octahedron=air
tetrahedron=fire
icosahedron=water
dodecahedron=ether

EmpedoclesofAgrigentum(492432B.C.)
Credited
Creditedwiththefirstannouncementoftheconceptof
with the first announcement of the concept of
fourelements:earth,air,fire,and water,whichwere
capableofcombiningtoformallothersubstances.
Elementscombinedbyspecificattractionsorrepulsions
Elements combined by specific attractions or repulsions
whichweretypifiedaslove andhate.

 AnaxagorasofKlazomenae(c.500428B.C.)
Considered
Consideredtheuniversetobecomposedofaninfinite
the universe to be composed of an infinite
varietyofsmallparticlescalledseeds.
Theseseedswereinfinitelydivisibleandpossesseda
quality which allowed "like to attract like" to form
qualitywhichallowed"liketoattractlike"toform
substancessuchaflesh,bone,gold,etc.

Leucippus(5thcenturyB.C.)andDemocritus(460
370B.C.)
Firstatomictheory.
Allmaterialthingsconsistedofsmallindivisibleparticles,
g
p
,
oratoms,whichwereallqualitativelyalike,differing
onlyinsize,shape,positionandmass.
Atoms,theystated,existinavacuousspacewhich
,
y
,
p
separatesthemand,becauseofthisspace,theyare
capableofmovement.(Thiscanbeconsideredatthe
firstkinetictheory.)

 PierreGassendi(15921655)
Revivedtheatomictheory(1650)
Atomsareprimordial,impenetable,simple,
unchangeable,andindestructiblebodies
Theyarethesmallestbodiesthatcanexist
Atomsandvacuum,theabsolutelyfullandthe
absolutelyempty,aretheonlytrueprinciples
y
p y,
y
p
p
andthereisnothirdprinciplepossible.
Atomsdifferinsize,shapeandweight
Atomsmaypossesshooksandother
Atoms may possess hooks and other
excrescences
Atomspossessmotion
Atomsformverysmallcorpuscles,or
Atoms form very small corpuscles or
molecules,whichaggregateintolargerand
largerbodies

 RobertBoyle(16271691)
H
Hypothesizedauniversalmatter,theconcept
h i d
i
l
h
ofatomsofdifferentshapesandsizes
Definedanelement(TheSceptical Chymist,
1661)
And,topreventmistakes,Imustadvertise
You,thatInowmeanbyElements,asthose
Ch i t thatspeakplainestdobytheir
Chymists
th t
k l i t d b th i
Principles,certainPrimitiveandSimple,or
perfectlyunmingledbodies;whichnot
being made of any other bodies or of one
beingmadeofanyotherbodies,orofone
another,aretheIngredientsofwhichall
thosecalld perfectlymixt Bodiesare
immediately compounded, and into which
immediatelycompounded,andintowhich
theyareultimatelyresolved.
Hecouldnotgiveanyexamplesofelements
that fit his definition.
thatfithisdefinition.

 SirIsaacNewton(1642
Sir Isaac Newton (1642 1727)
1727)
Modifiedatomictheorytoatoms
ashardparticleswithforcesof
attractionbetweenthem

EventsLeadingtotheModernAtomicTheory
StephenHales(16771761)
Devisedthepneumatictrough,
1727
Allowedforgenerationand
collectionofgases

JosephBlack(17281799)
Mass
Massrelationshipsinchemical
relationships in chemical
reactions,1752
Magnesiaalbaandfixedair.

MgCO3 MgO+CO
MgO + CO2

 HenryCavendish(1731
Henry Cavendish (17311810)
1810)
Inflammableair,Hydrogen,1766
Later:H2 +O2 H2O

JosephPriestley(17331804)
and
Carl Wilhelm Scheele (1742 1786)
CarlWilhelmScheele(17421786)
Dephlogisticatedair/feuerluft
Oxygen,1774

 Antoine
AntoineLaurentLavoisier
Laurent Lavoisier
(17431794)(andMarie
Anne Pierrette Paulze
AnnePierrettePaulze
Lavoisier(17581836)?)
Natureofcombustion,1777
Nature of combustion 1777
ElementsinTrait
lmentaire de chemie, 1789
lmentairedechemie,1789

TheAtomicTheoryy
JohnDalton(17661844)
NewSystemofChemical
Philosophy,1808
Allbodiesareconstitutedofavast
All bodies are constituted of a vast
numberofextremelysmall
p
particles,oratomsofmatterbound
,
togetherbyaforceofattraction
Theultimateparticlesofall
homogeneousbodiesareperfectly
alikeinweight,figure,etc.

The Atomic Theory

TheAtomicTheory
Atomshavedefiniterelativeweightsexpressedin
to s a e de te e at e e g ts e p essed
atomsofhydrogen,eachofwhichisdenotedby
unity
Atomscombineinsimplenumericalratiostoform
compounds
Undergivenexperimentalconditionsaparticular
U d
i
i
t l
diti
ti l
atomwillalwaysbehaveinthesamemanner
Atomsareindestructible
Atoms are indestructible

Daltonssymbols,1808
l
b l

Daltonsatomicweights,
l
h
1808

Jon Jakob Berzelius, 1813: Letters for element symbols

Name

Symbol

Name

Symbol

Name

Symbol

Name

Symbol

Oxygen

Tungsten

Tn

Palladium

Pa

Uranium

S l h
Sulphur

A i
Antimony

Sb

Sil
Silver

A
Ag

C i
Cerium

C
Ce

Phosphorus

Tellurium

Te

Mercury

Hg

Yttrium

Columbium
Cl
(nioblium)

Copper

Cu

Glucinum
(beryllium)

Gl

Titanium

Ti

Nickel

Ni

Aluminum

Al

Boron

Zirconium

Zr

Cobalt

Co

Magnesium Ms

Carbon

Silicium

Si

Bismuth

Bi

Strontium

Sr

Nitric radicle N

Osmium

Os

Lead

Pb

Barytium

Ba

Hydrogen

Iridium

Tin

Sn

Calcium

Ca

Arsenic

As

Rhodium

Rh

Iron

Fe

Sodium

So

y
Mo
Molybdenum

Platinum

Pt

Zinc

Zn

Potassium

Po

Chromium

Gold

Au

Manganese Ma

Muriatic
radicle
(chlorine)
Fluoric
radicle

Ch

PiecesofAtoms theelectron
HeinrichGeissler
(18141879)

JuliusPlcker
(18011868)

Evacuatedtube
glowed,1859
Raysaffectedbya
Rays affected by a
magnet

 JohannWilhelmHittorf(18241914)
J h
Wilh l Hitt f (1824 1914)
Maltesecrosstube,1869
Raystravelinstraightline
Castshadowsofobjects

 WilliamCrookes(18321919)
William Crookes (1832 1919)
Verifiedpreviousobservations,1879
Causedpinwheeltoturn
C
d i h lt t
Composedofparticles

Havenegativecharge
Have negative charge

 JosephJohnThomson(18461940)
e/m=1.759x108 coulomb/gram 1897

 RobertMillikan(18681923)
Oildropexperiment 1909
e=1.602x1019 coulomb
N=6.062x1023 molecules/gmolecule

Pieces of Atoms theproton

PiecesofAtoms
the proton
EugenGoldstein(1850
Eugen Goldstein (18501930)
1930)
Canalrays 1886

Pieces of Atoms theneutron

PiecesofAtoms
the neutron
JamesChadwick(1891
James Chadwick (18911974)
1974)
Discoveredtheneutron 1932

TheSubatomicParticles
Particle

Symbol

Charge
coulomb

Mass
g

Relative
Charge

RelativeMass
amu

electron

0
1

e or e

1.602x1019

9.109x1028

0.0005486 0

proton

p or 11H

1.602x1019

1.673x1024

+1

1.0073

neutron

n or 01n

1.675x10
1
675 x 1024

1 0087
1.0087

Models of the Atom

ModelsoftheAtom
PhilippLenard(18621947)
Philipp Lenard (1862 1947)
Dynamids 1903

HantaroNagaoka(18651950)
Saturnianmodel 1904

 J.J.Thomson
Plumpudding 1904
PartlybasedonA.M.
Mayers(18361897)
floatingmagnetexperiment

A. M. Mayer

We suppose that the atom consists of a

number of corpuscles moving about in a
sphere of uniform positive
electrification
when the corpuscles are constrained to
move in one plane the corpuscles will
arrange themselves in a series of
concentric rings.
When the corpuscles are not constrained
plane,, but can move about in all
to one p
directions, they will arrange themselves in
a series of concentric shells
J. J. Thomson, 1904
Photo Reference: Bartosz A. Grzybowski,
Howard A. Stone and George M. Whitesides,
Dynamic self-assembly of magnetized,
millimetre-sized
illi t
i d objects
bj t rotating
t ti att a liliquidair
id i
interface, Nature 405, 1033-1036 (29 June 2000)

ErnestRutherford(18711937)
HansGeigerandErnestMarsden 1908
Geiger and Marsden were running
experiments on scattering of alpha
particles when passing through thin foils of
metals such as aluminum, silver, gold,
platinum, etc. A narrow pencil of alphaparticles under such conditions became
dispersed through one or two degrees and
the amount of dispersion,,varied as the
square root of the thickness or probable
number of atoms encountered and also
roughly as the square root of the atomic
weight of the metal used.
Recollections by Sir Ernest Marsden, J. B. Birks,
editor, Rutherford at Manchester, W. A. Benjamin
Inc., 1963

InadiscussionwithGeiger,regardingErnestMarsden,
Rutherford stated that IIagreedwithGeigerthatyoung
Rutherfordstatedthat
agreed with Geiger that young
Marsden,whomhehadbeentraininginradioactivemethods,
oughttobeginaresearch.Whynotlethimseeifany
particles can be scattered through a large angle? I did not
particlescanbescatteredthroughalargeangle?Ididnot
believetheywouldbe
RecollectionsbyErnestRutherford,J.B.Birks,editor,RutherfordatManchester,W.A.Benjamin
Inc 1963
Inc.,1963

Theobservations,however,ofGeigerandMarsden**onthe
scatteringofaraysindicatethatsomeofthe
i
f
i di
h
f h
particles,about
i l
b
1in20,000wereturnedthroughanaverageangleof90degrees
inpassingthoughalayerofgoldfoilabout0.00004cm.thick,
Itseemsreasonabletosupposethatthedeflexionthrougha
largeangleisduetoasingleatomicencounter,
**Proc.Roy.Soc.lxxxii,p.495(1909)
Proc. Roy. Soc. lxxxii, p. 495 (1909)
***Proc.Roy.Soc.lxxxiii,p.492(1910)

Fromtheexperimentalresults,Rutherforddeducedthatthe
positi e electricit of the atom as concentrated in a small
positiveelectricityoftheatomwasconcentratedinasmall
nucleusandthepositivechargeonthenucleushada
numericalvalueapproximatingtohalftheatomicweight.
RecollectionsbySirErnestMarsden,J.B.Birks,editor,RutherfordatManchester,W.A.
BenjaminInc.,1963

Itwasquitethemostincredibleeventthathaseverhappened
tomeinmylife.Itwasalmostasincredibleasifyouhadfired
a 15 inch shell at a piece of tissue paper and it came back and
a15inchshellatapieceoftissuepaperanditcamebackand
hityou.
RecollectionsbyErnestRutherford,J.B.Birks,editor,RutherfordatManchester,W.A.
BenjaminInc.,1963

The
The
Rutherford
AtomModel
The atom is mostly empty space with a dense nucleus
Protons and neutrons in are located in the nucleus
nucleus.
The number of electrons is equal to the number of
p
protons.
Electrons are located in space around the nucleus.
Atoms are extremely small: the diameter of a hydrogen
atom is 6.1 x 10-11 m (61 pm)

SymbolsofElements
y
Atomic mass (A no )
Atomicmass(Ano.)

12
6

Elementsymbol
l
b l

Atomicnumber(Zno.)
No.ofneutrons=Ano. Zno.

Isotopes
Atomsofthesameelementwithdifferentmasses.
Atoms
of the same element with different masses
Isotopeshavedifferentnumbersofneutrons.

11
C
6

12
C
6

13
C
6

14
C
6

Isotopic Masses of Hydrogen

IsotopicMassesofHydrogen
Symbol

1
1
2
1
3
1

Name

Atomicmass
amu

NaturalAbundance
%

H
H

Hydrogen

1.007825032

99.985

Deuterium

2.01401778

0.015

Tritrium

3.0160492675

trace

Isotopic Masses of Magnesium

IsotopicMassesofMagnesium
Symbol

Atomicmass
amu

NaturalAbundance
%

24
12

23.985042

78.99

Mg
g

25
12

Mg

24.985837

10.00

26
12

Mg

25.982593

11.01

MassesofIsotopes
determinedwithamassspectrometer
p

CalculationofAtomicWeights
g
((mass isotope
p 1 % abundance)) + ((mass isotope
p 2 % abundance)) +
At Wt =
100
At Wt Mg
M =

((23.985042 78.99)) + ((24.985837 10.00)) + ((25.982593 11.01))

100

At Wt Mg =

(1894.578468) + (249.85837) + (286.0683489)

100

At Wt Mg =

(2430.505187)
100

At Wt Mg = 24.305

Radioactivityand
Stabilityofthenucleus
Wilhelm Conrad Roentgen
1845-1923
Discovered x-rays - 1895

Barium
platinocyanide

HenriBecquerel(18521908)
R di ti
Radiationactivity,1896
ti it 1896

Uranium nitrate
Image of potassium uranyl
sulfate

Pierre Curie (1859-1906)

Marie Curie (1867-1934)
(1867 1934)
Radioactivity- 1898
Polonium - 1898
Radium - 1898
pitchblende

MarieCuriewithinsetphoto
ofPierreCurie

Radium bromide

ErnestRutherford(18711937)
,, 1903

In his lab at McGill University

University, 1903

Kinetics of Radioactive Decay

KineticsofRadioactiveDecay
Thehalflife(thetimeittakesforhalfofthe
atomspresenttodecay)is:
d
)i

0.693
0
693
= t1/2
k
Where: Nt =
N0 = 1
and ln 0.5 = -0.693

RadiocarbonDatingand
the Shroud of Turin
theShroudofTurin
14
7

N+ n
1
0

14
6

0
1

C+ e

GlennT.Seaborg(19121999)
g(
)
Extendingtheperiodictable