2

Theatom
The smallest part of an elementis an atom. lt usedto be thoughtthat atomsare indivisible they can be brokendown into but many different sub-atomic particles. atoms,with the exception hydrogen, made up of threefundamental All of are sub-atomic particles- protons,neutrons,and electrons. The hydrogen atom,the simplest atom of all, contains just one proton and one electron. The actualmassof a proton is ,/ 1.672 x.t o-z+g but it is assigned relative a value of l . The masi of a neutronis virtuallyidenticaland algq hasa relativeniass of 1' Compared a protonand a neutronan electronhas negligible to masswith a relativemassof only Neutrons are neutral fr. particles. electronhasa chargeof 1.602 x 10 1ecoulombi *hl.h ir assigned relative An a value of -i . frirroton carriesthesame chargeas an electronbut of an oppositesignso hasa relative valueof +1 . All atomsare neutralso mustcontainequal numbers of protonsand electrons.

SUMMARY RELATIVE OF MASSAND CHARGE

Particle Relativemass Relativecharge

SIZEANDSTRUCTURE ATOMS OF
Atomshavea radiusin the orderof 10-10 Almostall of the m. massof an atom is concentrated the nucleuswhich has a very in small radiusin the orderof 10 ra m. All the protonsand (collectively neutrons callednucleons) locatedin the are nucleus. The electrons to be found in energylevelsor shells are surrounding nucleus Much of the atom is empty space. the

electron

5x10-4

-1

SHORTHANDNOTATION FOR AN ATOM OR ION

CHARGE ATOMIC NUMBER Z

Equalto the numberof protonsin the nucleusand to the numberof electrons in the atom.The atomic number defines which elementthe atom belongs and consequently to its positionin the Periodic Table. Atoms have no chargeso n = 0 and this is left blank. Howeverby losingone or more electronsatoms become positive ions,or by gainingone or more electronsatoms form negativeions.

EXAMPLES
Symbol
;6e lQc ^2+ 2U-37.t17v'

Atomic number
n

Mass number o 40 37

Numberof protons 4 20 17

Number of neutrons
E

Numberof electrons 4 1B 1B

20 17

20 20

All atomsof the sameelementmustcontainthe samenumberof protons,howeverthey may containa different numberof neutrons'Such atoms are known as isotopes. Chemical propertiesare relatedto the number of electronsso isotopes the same of elementhave identicalchemicalproperties. Sincetheir massis different their physicalproperties such as densityand boiling point are different.

Examples of isotopes:

lH ?H ?H

tAC ,3C

?tOt ?|Ct.

RELATIVE ATOMIC MASS

Thetwo isotopes chlorine of occurin theratio 3:1.Thatis,naturally of occurring chlorine contains 75%1,Cl and 25% 1l Cl. Theweighted mean molarmass thus: is (75x35)+(25x37) -=cc.cgmot-' 100 andthe relative atomic mass 35.5.Accurate is values 2 d.p.for all the relative to atomic masses theelements givenin Table of are 5 of the IBdatabooklet. These thevalues are whichmustbe used whenper{orming calculations theexaminations. in

6 Atomic structure

Massspqctrometer relativeatomicmass and

MASSSPECTROMETER
Relativeatomic masses can be determinedusing a massspectrometCr. vapo1izedsampleis iniected into the instrument. A Atoms of the element are ionizedby being bombardedwith a stream'ofhigh e;rgy eleitrons in the ionization chamber. In practice the instrument set so that only ionswith a singlepositivecharge"are is for"med. The resulting unipositive ions pass through holes in parallel platesunder the influenceof an electric field wiere they are accelerated. ih" ion, are then deflected by an external magneticfield. The amountof deflection depends both on the massof the ion and its charge. The smallerthe massand the higherthe charge the greaterthe deflection. lons with a particularmass/charge ratio are theniecorded on a detectorwhich meazures both thJ massand the relativeamountsof all the ions present.

DIAGRAM A MASSSPECTROMETER OF
ion-accelerating voltaoe beam of lighter palticles

1 vaporizer

I
2ionizer

filament
3 accelerator and aligner 4 deflector
-_ti

beam of heavier particles 5 detector 6 recorder

TFE MASSSPECTRUM NATURALLY OF OCCURRTNG LEAD

USES RADIOACTIVE OF ISOTOPES

lsotopes have many usesin chemistryand beyond.Many, but by no meansall, isotopes of elementsare radioactive as the nuclei of theseatoms break down spontaneously. When they break down these radioisotopes it radiation em w h i c h i s d a n g e r o ut o l i v i n g s things.Thereare three differentforms of radiation. Camma (1)radiationis highly penetrating whereasalpha (o) radiation, can be stopped by a few centimetresof air and beta (0) radiationby a thin sheetof a l u m i n i u m .R a d i o i s o t o o e s n ca occur naturallyor be created artificially.Their usesinclude nuclearpower generation, the sterilization surgical of instruments hospitals, in crime detection,finding cracksand stresses metalsand the in preservationof food. 1fC is usedfor carbon dating,lorco is used in radiotherapy and lflt and 1(ll are usedas tracersin medicinefor treatingand diagnosingi Ilness.

203

204

205 206 207 masS/Charge

208

209

Therelative atomicmass leadeanbe calculated of fromthe weighted average:

lsotopic mass Relativeabundance % relative abundance
z

204 206 207 208

0.2
1A

24
zz

2.2 5.2

52

(2 x 2d4\+ (24 x206) + (22 x 207)+(52 x 208) ^^ -=--ry=2o7'2 relative atomicmass_ 100

-Atomic structure 7

Emission spectra
THEELECTROMAGNETIC SPECTRUM
Electromagnetic waves can travel through spaceand, dependingon the wavelength,also through matter.The velocity of travel c is relatedto its wavelengthl, and its frequency f Velocity is measuredin m s 1, wavelength in m and frequency in s 1 so it is easyto rememberthe relationshipbetween them: C=1,x f (ms-l) (m) (s-1)

Electromagnetic radiationis a form of energy The smallerthe wavelength and thusthe higherthe frequency the more energythe wave possesses. Electromagnetic waves have a wide range.ofwavelengthsrangingfrom low energy radio waves to high energy y-radiation. Visiblelight occupiesa very narrow part of the spectrum.

The visibleregionhas been expanded here.

f 5.5 x 1014 s-1 i 650 x 10-sm

9 . 5 x 1 0 1 4s - 1 400 x 10-s m

redOY visiblelight

106 radio waves long 103 medium

f/s-11012

10 1 5

10 1 8 y-radiation

llm

ATOMIC EMISSION SPECTRA

White light is made up of all the coloursof the spectrum. When it is passed througha prisma continuous spectrumof all the colourscan'be obtained. When energyis suppliedto individualelements they emit a spectrum wavelengths. which only contains emissions particular at Eachelementhas its own characteristic spectrum known as a line spectrumas it is not continuous. The visible hydrogen spectrum reo blue indigo violet convergence
-6() b-

pu L$6 w a v e l e n g t h , l , / nm

So odc8

s&

Note that the spectrumconsistsof discreteIinesand that the lines convergetowards the high energy (violet)end of the spectrum. A similarseries Iinesat even higherenergyalsooccursin the ultraviolet of regionof the spectrum other series lines of and several at lower energy can be found in the infraredregion of the spectrum.

EXPLANATION EMISSION OF SPECTRA

When energf is suppliedto an atom electrons are excited(gainenergy) from their lowest(ground) stateto an excitedstate.Electrons only existin certain can fixed energylevels. When electrons drop from a higher levelto a lower levelthey emit energy.This energy corresponds a particular to wavelengthand showsup as a line in the spectrOm. When electrons returnto the first level (n = 1) the series linesoccursin the of ultravioletregionas this involves the largest energy change.The visibleregionspectrumis formed by electrons droppingback to the n = 2 leveland the first seriesin the infraredis due to electrons fallineto the n = 3 level.The linesin the spectrum.onu"r!" because energylevelsthemselves the converge.

ll nm

656 (n=3--n=2)

486 (n= 4-n=2)

365 (n=*-n=2;

8 Atomic structure

Electron arrangement
EVIDENCE FROM IONIZATION ENERGIES
The first ionizationenergyof an elementis definedas the engrgy requiredto remove one electronfrom an atom in its gaseous state.It is measured kJ mol-1. in X(g)-X+(g)+eA graph of first ionization energiesplotted againstatomic number shows a repeatingpattern. It can be seenthat the highest value is for helium,an atom that containstwo protonsand two electrons.The two electronsare in the lowest level and are held tightly by the two protons.For lithium it is relativelyeasyto remove an electron, which suggests the third electronin lithium is that in a higherenergylevelthan the firsttwo. The valuethen generally increases until elementl0, neon, is reached before it dropssharplyfor sodium.This graphprovides evidence that the levelscan contain differentnumbersof electrons beforethey become full. Level 1 (Kshell) 2 (Lshell) 3 (M shell) Maximum number of electrons 2 B B (or 18)

for First ionizationenergies the first twentyelements f_ 2500

E -) i 2000 o

s) . - ^ ^ E
c o o

5 'ouu

F looo

E doo
6 8 1012 16

1 8 20

atomicnumber

ELECTRON ARRANGEMENT
The arrangement electronsin an atom is known as its electronicconfiguration.Eachenergy level or shell is separated a dot of by (or a comma). The electronsin the highestmain energy level (outermostlevel) are'known as the valence electrons. Element H He Li Be B
I

Electron configuration
I

2 (first level full) 2.1 2.2

z.J 1A

o
E

Ne

2.5 2.6 2.7 2.8 (second level full)

Element Na Mg AI Si P S CI K-t

Electron configuration 2.8.1 2.8.2. 2.8.3 2.8.4 2.8.5 2.8.6 2.8.7 2.8.8(third level full) 2.8.8.1 2.8.8.2

EVIDENCE FOR SUB-LEVELS

The graphalreadyshown abovewas for the first ^ 6.0 ionizationenergyfor the first twenty elements. SuccessiveT ionizationenergies the sameelementcan also be for measured, e.g.the secondionizationenergyis given by: 5 +.0 X*(g) X2*(g)+eAs more electronsare removed the pull of the protons holdsthe remaining electrons more tightly so increasinglymore energy is requiredto removethem, hencea logarithmic scaleis usuallyused.A graphof the successive ionizationenergies potassium for also providesevidenie of the number of electronsin each main level.

E s.o
I P 3.0 (!)

6 z.o 'Er.o o
8o
1 21 3 1 4 1 5 1 6 1 7 1 8 1 9 01234567891011 removed numberof electronS

jump' occursin successive By lookingto seewhere the first''large the ionizationenergies one can determine (and hencethe group in the Periodic numberof valenceelectrons Tableto which the elementbelongs). lf the graph for first ioniTationenergiesis examined more closely then it can be seenthat the graph does not increaseregularly. This provides evidence that the main levelsare split into sub-levels.

I Atomic structure

ffi

Sub-levels orbitals and

TYPESOF ORBITAL
Electrons found in orbitals. are Eachorbitalcan containa maximumof two electrons eachwith opposite spins.The first level just one orbital,calledan s orbital.The secondlevelcontains contains one s orbitaland threep orbitals. The 2p orbitalsare all of equal energybut the sub-level made up of thesethree2p orbitalsis slightlyhigherin energythan the 2s orbital.This explains why the first ionizationenergyof B is lower than Be as a higherenergy2p electronis being removedfrom the B comparedwith a lower energy2s electronfrom Be. Principal level (shell) Number of each type of orbital
qrn A l -

Maximum number of electrons in level

1 2 3
4

t13 1357

2 B 1B
.)1

Relative energies of sub-levels within an atom

-.--{d-

The relative positionof all the sub-levels the firstfour main energylevelsis shown. for Note that the 4s sub-level below the 3d sub-level. is This explains whv the third level is sometimesstatedto hold B or I B electrons. e Electrons with opposite spinstend to repeleach other.when orbitalsof the sameenergy p' (degenerate) filled the electrons are will go singlyinto each orbitalfirstbeforethey pair up 6 to minimize repulsion. This explains why there is a regularincrease the first ionization in energies goingfrom B to N as the three2p orbitalseachgain one electron. Then there is a slightdecrease betweenN and O as one of the 2p orbitals gainsa secondelectronbeforea regularincrease again.

+s-4!-3; 3p x2p

-g?-

4t

I J

SHAPESOF ORBITALS
An electronhasthe properties both a particleand a wave of Heisenberg's uncertainty principlestates that it is impossible to know the exactpositionof an electronat a precisemomentIn time. An orbitaldescribes three-dimensional the shapewnere there is a high probability that the electronwill be located. s orbitalsare spherical and the three p orbitalsare orthogonal (at right angles) each other. to

AUFBAU PRINCIPLE
The electronic configuration can be determined followingthe aufbau(buildingup) principle.The orbitals by with the lowest energyare filled first.Eachorbitalcan containa maximumof two electrons. Orbitalswithin the samesub-shell filled singly are first- this is known as Hund's rule. e.g. F 1s22s22ps v 1s22s22p%s23p64s236s.

To savewriting out all the lower levelsthe configuration may be shortened buildingon the lastnoble gasconfiguration, by e g. V is more usuallywritten: lArl 4s2gd3. (Whenwriting electronic configurations checkthat for a neutralatom the sum of the superscripts addsup to the atomic number of the element.) Sometimes boxesare usedto represent orbitalsso the numberof unpaired electrons can easilybe seen,

C 1s22s22o2 '

ls T{Tl rr
I I

ELECTRONIC CANFIGURATION ANDTHE PERIODIC TABLE

positionin the Periodic An element's Table is related its to valenceelectrons the electronic so configuration anv element of can be deducedfrom the Table,e.g. iodi"ne (Z= 53) is a p block element.lt is in group 7 so its configuration will containns2np5. lf one takesH and He as beingthe first periodthen iodine is in the fifth periodso n = 5. The full configuration iodinewill for thereforebe: 1s22s22p03"23p64s23d104p65s24d105p5 5s24d105p5 or IKr]

10 Atomic structure