overhead chapter 1

8/3/2019 Overhead Chapter 1

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WilliamRowanHamilton18051865

ZeranColburnAmericanchildprodigy


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"Heusedtocarryonlongtrainsofalgebraicandarithme8calcalcula8onsinhismind,duringwhichhe

wasunconsciousoftheearthlynecessityofea8ng..."

WilliamEdwinHamilton(hiselderson)

Rowanandson

Whowouldnotratherhavethefame

ofArchimedesthanthatofhis

conquerorMarcellus?


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1868MapofLafaye>e,Indiana

FirstUSAirmailFlight,Lafaye>e,Indianain1859


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1878MapofChaunceyshowingPurdueUniversityGrantSt. Northwestern

University

Hall

PurdueUniversitywasfoundedin1869.Classesstartedin1874.

ThefirstdegreewasaBachelorofScienceinChemistryawardedin1875.

Competed

in1874


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1862Rail-RoadandMilitaryMapoftheUS


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JosiahWillardGibbs

1839-1903

Oneoftheprincipalobjectsoftheorecalresearchinanydepartmentofknowledge

istofindthepointofviewfromwhichthesubjectappearsinthegreatestsimplicity.


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Max Karl Ernst Ludwig Planck1858 - 1947

19011878

Sciencecannotsolvetheulmatemysteryofnature.Andthatisbecause,inthe

lastanalysis,weourselvesareapartofthemysterythatwearetryingtosolve.


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FromthePrefacetoGibbsStascalMechanics(1901)


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HeatCapaciesofGasesandSolids

Diamond

Theobservedtemperaturedependenceimpliesthat

molecularvibraIons(androtaIons)

arequanIzed,justlikephotons! Energy

LowT HighT

Inacve Acve

Classicalpredic8on:

U=aT

Heat

Capacity:

Cv=(dU/dT)v

=a

ExpectCVtobe

T-independentBoltzmann

distribuWon = h


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Albert Einstein1879- 1955

Themostincomprehensiblethinkabouttheworldis

thatitiscomprehensible.

192118931904


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AlbertEinsteinsRelavityandE=mc2(1905)

Atom velocity

m = E/c2


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PhotoelectricEffect


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=hphotonenergy

Frequency

oflight

EinsteinsExplanaonofthePhotoelectricEffect(1905)

Plancks

Constant


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Movie

EinsteinsExplanaonofBrownianMoon(1905)

ProvedthatmoleculesreallyexistDeterminedAvogadrosnumber,NA

Mean-squared

displacementRadius Viscosity Time

Allofthesequan88esare

experimentallymeasurable

Animation


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What Happened in Lubeck in 1895?

A shouting match between the atomist and the energist

Which was which?Who won the day?

WilhelmOstwald LudwigBoltzmann


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GeorgHelm(speaker,wrotetohiswife):

Thegreatac8vityliesbehindme.Ibelievethatthelecturewasasuccess,itwasapplaudedandpraised;

butduringthediscussiontherewasas8fffight.

Boltzmanncommencedwithfriendlyapprecia8ve

remarksand[then]begantoinveighagainst

OstwaldsandmyworkOstwaldandBoltzmanncame

toheavyblowsThemee8nglastedfrom9un8laer

12Thehallwasmorethanhalffull,sothatafew

hundredpersonsexperiencedthewholebusiness

Personal Accounts of the Lubeck Conference

ArnoldSommerfeld(audiencemember):

Thechampionofenerge8cswasHelm;behindhimstoodOstwaldandbehindbothofthemthephilosophy

ofMach(whowasnotpresentinperson).Thebale

betweenBoltzmannandOstwaldwasmuchliketheduel

ofabullandasupplebullfighter.However,this8methe

bulldefeatedthetoreadorinspiteofallhisagility.The

argumentsofBoltzmannstruckthrough.Weyoung

mathema8cianswereallonBoltzmannsside

Ostwald(recountedyearslater):Atthediscussion[inLubeck]Ifoundmyselfbeforea

closedantagonism.Myonlysupporterandfigh8ng

companionwasGeorgHelm.Buthewasremovedfrom

mebecauseofhisaversiontoarealis8cconcep8onof

energyItwasthefirst8methatIpersonallyfound

myselfconfrontedbysuchaunanimousbandofdownrightadversaries

(inhisbookwrienin1909):[Boltzmannis]themanwhoexcelledallofusinacumen

andclarityofhisideas.

Boltzmann(GasTheory,PartII,19):WhenthefirstpartofGasTheorywasbeingprinted[in195]

Itwasjustatthis8methataacksonthetheoryofgases

begantoincrease.Iamconvincedthattheseaacksare

merelybasedonmisunderstanding,andthattheroleofgas

theoryinsciencehasnotyetbeenplayedoutInmyopinionit

wouldbeagreattragedyforscienceifthetheoryofgases

weretemporarilythrownintooblivionbecauseofamomentaryhos8leatudetowardit,aswasforexamplethe

wavetheorybecauseofNewtonsauthorityIamconsciousof

beingonlyanindividualweaklystrugglingagainstthestream

of8me.


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Einstein(leertoOstwald,1901):

EsteemedHerrProfessor!Becauseyourbookongeneralchemistry

inspiredmetowritetheenclosedar8cle,Iam

takingthelibertyofsendingyouacopyofit.On

thisoccasionpermitmealsotoinquirewhether

youmighthaveuseforamathema8calphysicist

familiarwithabsolutemeasurements...becauseI

amwithoutmeans,andonlyaposi8onofthis

kindwouldoffermethepossibilityofaddi8onal

educa8on.

Respecullyyours,AlbertEinstein

(givestheaddressofhisparents)

Threeweekslaterhewroteagain:

EsteemedHerrProfessor!

AfewweeksagoItookthelibertyofsending

youfromZurichashortpaperwhichIpublishedin

Wiedemann'sAnnalen.Becauseyourjudgment

ofitmaersverymuchtome,andIamnotsure

whetherIincludedmyaddressintheleer,Iam

takingthelibertyofsendingyoumyaddress

hereby.Respecully...

EinsteinsFather(leertoOstwald,1901):EsteemedHerrProfessor!

Pleaseforgiveafatherwhoissoboldastoturntoyouin

theinterestofhisson.Ishallstartbytellingyouthatmy

sonAlbertis22yearsold,thathestudiedattheZurich

Polytechnikumfor4years,andthathepassedhisdiploma

examina8onsinmathandphyswithflyingcolorslast

summer.Sincethen,hehasbeentryingunsuccessfullyto

obtainaposi8onasanAssistant,whichwouldenablehim

tocon8nuehiseduca8onintheore8cal&experimental

physics.Allthoseinposi8ontogiveajudgmentinthe

maer,praisehistalents;inanycase,Icanassureyouthat

heisextraordinarilystudiousanddiligentandclingswith

greatlovetohisscience.

Mysonthereforefeelsprofoundlyunhappywithhis

presentlackofposi8on,andhisideathathehasgoneoff

thetrackswithhiscareer&isnowoutoftouchgetsmore

andmoreentrenchedeachday.Inaddi8on,heis

oppressedbythethoughtthatheisaburdenonus,peopleofmodestmeans.

Sinceitisyou...whommysonseemstoadmireand

esteemmorethananyotherscholarcurrentlyac8vein

physics...[Imake]thehumblerequesttoreadhis

paper...andtowritehim,ifpossible,afewwordsof

encouragement,sothathemightrecoverhisjoyinliving

andworking

Why did Einstein Write to Ostwald?


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FromtheprefacetoOutlinesofGeneralChemistrybyW.Ostwald(1912).

BoltzmannsandEinsteinstheore8calcontribu8onsareacknowledgedonp.45.

Ostwald Accepts the Atomic Hypothesis

I am now convinced that we have recently become possessed of

experimental evidence of the discrete or grained nature of maer,

which the atomic hypothesis sought in vain for hundreds and

thousandsofyears.Theisola8onandcoun8ngofgasions,ontheone

hand, which have crowned with success the long and brilliant

researchesofJ. J.Thomson,and,ontheother,theagreementoftheBrownianmovementswiththerequirementsofthekine8chypothesis,

establishedbymany inves8gators andmost conclusively byJ.Perrin,

jus8fythemostcau8ousscien8stinnowspeakingoftheexperimental

proofof the atomic nature ofmaer. The atomic hypothesis is thus

raisedtotheposi8onofa scien8ficallywell-founded theory,and can

claim its place in a text-book intended as an introduc8on to the

presentstateofourknowledgeinGeneralChemistry.


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Einsteins Miracle Year (1905)

Einstein:NobelPrizeinPhysics1921"forhisservicestoTheore8calPhysics,andespecially

forhisdiscoveryofthelawofthephotoelectriceffect"

Relativity E=mc2 Light Particles Brownian Motion

The first person that Ostwald nominated for a Nobel Prize was Albert Einstein

Ostwald:NobelPrizeinChemistry"inrecogni8onofhisworkoncatalysisandforhis

inves8ga8onsintothefundamentalprinciplesgoverning

chemicalequilibriaandratesofreac8on"

Ostwalds Nobel Prize (1909)


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LineSpectraofAtomsandMolecules

MoleculesappeartohavequanIzedenergies!

RotaonofCO2 VibraonsofaNano-Ice-Cube


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In1912Neilswrotetohisbrother,Harald:

Thingsaregoingratherwell,forIbelieveIhavefoundoutafewthings;but,

tobesure,IhavenotbeensoquicktoworkthemoutasIwasstupidtothink.

NielsHenrikDavidBohr

(1885-1962)


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EnergiesofPhotonsandMolecules

Figure1.2inUnderstandingPhysicalChemistry


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Wave-ParIcleDuality

AlbertEinstein LouisdeBroglie

=h=hc/Momentum

PlancksConstant

p=h/Energy

Frequency Wavelength


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DiffracIonofWaves

ThomasYoung'ssketchoftwo-slitdiffrac8on103.


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DiffracIonofElectrons

DiscoveredaccidentallybyDavissonandGermer1927atBellLabs


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MolecularDiffracIonHeandH2byRocksalt

ExperimentalDataofOoStern19301943

1913

DuringtheyearthatStern

spentasEinsteinsfirst

postdoctoralassociate

Stern Einstein


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rwinSchroedinger

DevelopedWaveEquaIonWhichPredicts

QuanIzaIonofAtomic&MolecularEnergies


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VibraIonalNormalModesofaString


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2-DVibraIonalNormalModes


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3-DNormalModes

x

yz


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StaIsIcallyndependentProbabiliIesMulIply

P()=P()P()=1/6x1/6=1/36

P()=P()P()=1/2x1/2=1/4

Molecular

KineIc

Energies

x=

1

2mv

x

2

y

=1

2mv

y

2

z=

1

2mv

z

2

P(x +y +z) = P(x )P(y )P(z )

P(i) eci

P(x +

y +

z) e

c(x +y +z ) e

cxecxe

cz P(x )P(y )P(z)

So,


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BarometricDistribuIonofAtmosphericDensity

Use,idealgaslaw

andgravitaIonal

potenIalenergy

=

mgh

Toobtain,

P()

0

= emgh / kBT

= e / kBT

1/kBTSo,

Height,h

Denisty, !!0

!(h)


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Eq.1.24inUPC

= h

=1/kBTor1/RT

overhead chapter 1

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