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Chapter 8

Chapter 8
The Quantum Mechanical Atom
The Quantum Mechanical Atom
Achmad Rochliadi
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Summary Highlight
Summary Highlight

Model of Atomic Theory

Electromagnetic Energy

Atomic Spectra

Matter Wave

Electron Configuration

Shape of !r"ital

Atomic propertie
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Atomic Model #re $8%%
Atomic Model #re $8%%

&emocritu '

(ature of thing conit of an infinite num"er of


e)tremely mall particle* +hich they called atom,

Atom are phyically* "ut not geometrically*


indivii"le,

Atom are indetructi"le and completely full* i,e,


containing no empty pace, -ecaue of their
indetructi"ility* atom are eternal, .
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&alton '

Each element i compoed of mall particle


called atom,

Atom are neither created nor detroyed in


chemical reaction,

All atom of a given element are identical

Compound are formed +hen atom of more


than one element com"ine
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Thompon '

The atom of the element conit of a


num"er of negatively electrified
corpucle encloed in a phere of
uniform poitive electrification,
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Rutherford

The atom of an element conit of a mall* poitively


charged nucleu in the centre* +hich carrie almot the
entire ma of the atom,

The electron are revolving around the nucleu at high


peed,

The num"er of electron in an atom i e/ual to the


num"er of proton, Hence it i electrically neutral,

The volume of the nucleu i negligi"ly mall


compared to the volume of the atom,

Mot of the pace in the atom i empty


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Rutherford Simple &eign
Rutherford Simple &eign
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(iel -ohr'

Atom i a mall* poitively charged nucleu


urrounded "y electron that travel in circular
or"it around the nucleu0imilar in tructure
to the olar ytem* "ut +ith electrotatic force
providing attraction* rather than gravity,
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The Quantum Mechanical Atom
The Quantum Mechanical Atom

-y the late $8%%1 it +a clear that claical


phyic +a incapa"le of decri"ing atom
and molecule

E)periment ho+ed that electron acted


li2e tiny charged particle in ome
e)periment and +ave in other

The phyic that decri"e o"3ect +ith


wave/particle duality i called quantum
mechanics or quantum theory
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Energy can "e tranferred "et+een thing a


light or radiation

Radiation carrie energy through pace a


waves or ocillation moving out+ard from
a ditur"ance

Electromagnetic +ave 4radiation5 may "e


characteri6ed "y their .height7 or
amplitude and the num"er that occur per
econd or frequency 4v5
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11
8ight Act A A Wave
8ight Act A A Wave

Wavelength () the ditance light travel to


complete one cycle

Frequency () the num"er of +ave cycle


in one econd

unit are cycle per econd 4cp5* Hert6 4H65

H6 9
:$
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Electromagnetic radiation provides the clue to the electronic structures of
atoms
12
Frequency And Wavelength Are Related
Frequency And Wavelength Are Related

(ote that a the fre/uency of the +ave


increae* the +avelength decreae

Regardle of the fre/uency* light travel at


the ame peed* c

c9;<=

the speed of light (c) 9 >,??@?>AB8 < $%


8
mC

Learning Check' Df the fre/uency of a radio


tation i E%%, MH6* +hat i the +avelength
in mF
0.999 m
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7.1 Electromagnetic radiation provides the clue to the electronic structures
of atoms
13
Radiant nergy !pectrum
Radiant nergy !pectrum
high energy,
short waves
low energy,
long waves
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@,$ Electromagnetic radiation provide the clue to the electronic tructure of atom $A
"hotoelectric ffect #"article $heory %f
"hotoelectric ffect #"article $heory %f
Light&
Light&

Al"ert Eintein 4$?%B5 E9h=

Shining light on a clean metal urface may


e3ect electron

There i a threhold level needed to e3ect the


electron 4a +or2 function pecific to the
metal5

Dncreaing intenity doe not caue the effect

Dncreaing the frequency of the light doe


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The unit of fre/uency are the hert' 4('5


The minimum and ma)imum amplitude of


electromagnetic radiation are evenly paced

The pea2:to:pea2 ditance i called the


wavelength
5 econd C4 $ C $ $ H6 $
:$
= = =
5 4
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The product of fre/uency and +avelength


give the peed of light 4c5

Electromagnetic radiation come in a "road


range of fre/uencie called the
electromagnetic spectrum

The electromagnetic pectrum i divided


into region according to the +avelength
of radiation
mC $% E,%%
8
= = c u
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What +e call light i a mall lice of the


electromagnetic pectrum +ith +avelength
"et+een a"out A%% and @%% nm

Thi i called the visi)le region "ecaue +e can


.ee7 thee +avelength of the electromagnetic
pectrum

Gamma ray* H ray* and ultraviolet radiation


have +avelength horter than the vii"le region

Micro+ave* infrared radiation* and radio +ave


have +avelength longer than vii"le light
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The +ay a u"tance a"or"


electromagnetic radiation can "e ued to
characteri6e it

Ior e)ample* each u"tance a"or" a


uni/uely different et of infrared
fre/uencie

A plot of +avelength a"or"ed veru the


a"orption i called an infrared a)sorption
spectrum

Dt can "e ued to identify a u"tance


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The ocillating magnetic and electric field


of an electromagnetic +ave interact +ith
particle that it pae

A charged particle can pic2 up energy at the


e)pene of the radiation ource
Infrared
asorption
spectrum
of wood
alcohol
!methanol"
.
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The energy tranfer i not decri"e correctly


"y claical phyic

Dn $?%% the German cientit Ma) #lanc2


propoed that the electromagnetic radiation
could "e vie+ed a a tream of tiny energy
pac2et or quanta +e no+ call photons

#hoton travel at the peed of light

#lanc2 propoed* and Eintein confirmed*


that the energy of a photon is proportional
to its frequency
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Thi mean that )oth electron and


electromagnetic radiation can "e
repreented a either +ave or particle

The vii"le pectrum i a continuous


pectrum "ecaue it contain a continuou
ditri"ution of light of all color

E)cited atom can emit light


J $% K,K>K contant #lanc2L
photon of energy
EA :
= =
= =
h
h E v
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>>
Ilame Emiion
Ilame Emiion

Element e)hi"it characteritic color +hen


"urned

The characteritic pectra are alo o"erved


+hen element are u"3ect to trong electrical
field a in ga dicharge tu"e,
(ote that the
light from the
dicharge tu"e i
actually everal
different colored
line a een on
the urface of the
C&
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The atomic spectrum or emission


spectrum i a erie of individual line
called a line spectrum

Atomic pectra are uni/ue for each element


#ight emitted y
e$cited atoms is
comprised of a
few narrow eams
with fre%uencies
characteristic of
the element.
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Dn general* the line pectrum of an element


i rather complicated

The line pectrum of hydrogen* +ith a


ingle electron* i the implet

The Ryd)erg equation can "e ued to


calculated all the pectral line of hydrogen
n
1
and n
>
are poitive integers
#attern Dn Atomic 8ine Spectra
$

=R
H
(
$
n
$
>

$
n
>
>
)
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The Ryd"erg contant* R
H
* i an empirical
contant +ith a value of $%?*K@8 cm
:$

Atomic line pectra tell u that when an


excited atom loses energy, not just any
arbitrary amount can be lost

Thi i poi"le if the electron i retricted


to certain energy levels

The energy of the electron i aid to "e


quanti'ed
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The firt theoretical model that uccefully


accounted for the Ryd"erg e/uation +a
propoed in $?$E "y (iel -ohr
&ontinuous !a" and discrete
!" potential energy of a
tortoise. 'he potential energy
of the tortoise in !" is
%uanti(ed.
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie >8

Electron move around the nucleu in fi)ed


path or orbits much li2e the planet move
around the un

!r"it poition* la"eled +ith the integer n*


have pecific potential energy

The lo+et energy tate of an atom i called


the ground state 4an electron +ith n 9 $ for a
hydrogen atom5
-ohr1 Model !f The Atom
-ohr1 Model !f The Atom
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie >?
A"orption And Emiion
A"orption And Emiion

Electron that
absorb energy are
raied to a higher
energy level

A particular
fre/uency of light i
emitted +hen an
electron fall to a
lo+er energy level
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E%

Thi e/uation allo+ the calculation of the energy*


E* of any or"it

"9 -ohr1 contant

n i the or"it location


J $% >,$8 "
n
"
E
$8
>

=
=
-ohr E/uation 4$?$E5
-ohr E/uation 4$?$E5
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E$

-ohr1 4theoretical5 e/uation e)plain the


e)perimental 4empirical5 Ryd"erg e/uation

The com"ination of contant* b/hc* ha a


value +hich differ from the e)perimentally
derived value of R
H
"y only %,%BMN
( )
( ) ( )
> >
> >
> >
$ $ $ $
$ $
or
+ith
5 4
h l
h l
l h
n n
hc
b
l h
n n
n
b
n
b
l h
hc
n n b
E E E
= =
> =
= = A


-ohr1 Model #redict Energy 8evel
-ohr1 Model #redict Energy 8evel
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie E>
Oour TurnN
Oour TurnN
Which energy i not poi"le according to -ohr1
ModelF
A, :B,B<$%
:$?
J
-, :$,A<$%
:$?
J
C, :$,8<$%
:$?
J
&, none of thee
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@,> Atomic line pectra are evidence that electron in atom have /uanti6ed energie EE

Theory +a not
a"le to e)plain
the pectra of
atom +ith more
than one electron

Theory doen1t
e)plain the
collaping atom
parado)
-ohr1 Model Iail
-ohr1 Model Iail
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@,E Electron have propertie of "oth particle and +ave EA
8ight E)hi"it Dnterference
8ight E)hi"it Dnterference

Constructive interference: +ave .in:


phae7 create +ave of greater amplitude
4 they add5

estructive interference: +ave .out:of:


phae7 create +ave of lo+er amplitude
4they cancel out5
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@,E Electron have propertie of "oth particle and +ave EB

8ight e)hi"it interference* and it alo ha


particle nature

Electron* 2no+n to "e particle* alo


demontrate interference
&iffraction And Electron
&iffraction And Electron
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An electron that .ecape7 from the nucleu


ha infinity for it /uantum num"er and
6ero energy

-ohr1 4theoretical5 e/uation e)plain the


4empirical5 Ryd"erg e/uation
( )
( ) ( )
> >
> >
> >
$ $ $ $
$ $
or
+ith
5 4
h l
h l
l h
n n
hc
b
l h
n n
n
b
n
b
l h
hc
n n b
E E E
= =
> =
= = A


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The com"ination of contant* b/hc* ha a


value +hich differ from the e)perimentally
derived value of R
H
"y only %,%BM

-ohr1 effort to develop a general theory


of electronic tructure +a doomed "y the
+aveCparticle duality of electron

&e -roglie uggeted that the +avelength


of a particle of ma m moving at peed v i
mv
h
=
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Thi relation provide the lin2 "et+een the


decription a a particle and a a +ave

Heavy o"3ect have very .hort7


+avelength o their matter +ave and the
+ave propertie go unnoticed

Tiny particle +ith mall mae have


.long7 +avelength o their +ave propertie
are an important part of their "ehavior

Wave com"ine in t+o +ay


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The contructive and detructive


interference i called diffraction

Electron produce imilar pattern


!a" )aves in phase interfere constructively. !" *ut of phase
waves produce destructive interference. !c" )aves passing
through holes fan out and produce an interference pattern.
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There are t+o type of +ave' traveling


and standing

A tanding +ave i produced +hen a guitar


tring i pluc2ed' the center of the tring
vi"rate* "ut the end remain fi)ed

#oint of 6ero +ave amplitude are called


nodes
'he wind produces
traveling waves on the
surfaces of la+es and
oceans.
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Ior guitar tring the only +ave are thoe


for +hich a half:+avelength i repeated
e*actly a +hole num"er of time

Ior a trength of length +ith n an integer


thi can "e +ritten
,tanding waves on a guitar
string.
( )
n

n
>
>
' g rearrangin or = =

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Thee reult can "e ued to ho+ ho+


/uantum theory unite the +ave and particle
decription of a "ound electron

Conider the claical particle model of the


."ead on a +ire7

Df the electron 4particle5 ha ma m and


peed v

The 2inetic energy of the moving electron i


>
>
$
mv E =
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The &e -roglie relation connect model


4a5 and 4"5
!a" - classical model of the
electron as a ead on a wire. -ny
energy is possile and position is
e$actly +nown. !" &lassical
model of the electron as a
standing wave. !c" .uantum
mechanical model comines !a"
and !". /ar+ areas indicate
proale electron positions.
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The electron energy i /uanti6ed "ecaue it


depend on the integer n

The lo+et energy allo+ed i for n9$ or


E!h
"
/#m
"
4the energy cannot )e 'ero5
( )
>
>
>
>
>
8
>
>
>
>
$
>
>
$
give uing
' ng u"tituti or
m
h n
n

m
h
m
h
m
h
mv
h
E
m mv E
v
= =
= = =
= =

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Electron trapped on a +ire have ome


reidual 2inetic energy* 3ut li2e electron
trapped in atom
'he spacing
etween levels is
proportional to 10#
2
.
!a" - long wire. !"
- short wire. 'he
longer the wire, the
smaller the spacing
etween allowed
energy levels.
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The +ave that correpond to the electron i


called a wave function

The amplitude of the +ave function at a


given point can "e related to the
pro)a)ility of finding the electron there

According to /uantum mechanic there are


region of the +ire +here the electron +ill
not "e found

Region of 6ero +ave function amplitude


are called node
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Dt i generally true that the more nodes an


electron has, the higher its energy

Er+in SchrPdinger +a the firt to


uccefully apply the concept of the +ave
nature of matter to electronic tructure

He developed an e/uation that can "e


olved to give +ave function and energy
level for electron trapped in them

Wave function for electron in atom are


called or)itals
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!r"ital are characteri6ed "y a et of three


/uantum num"er'
n 9 principle /uantum num"er, All
or"ital +ith the ave principle
/uantum num"er are in the ame shell,
Allo+ed value' the et of poitive
integer,
l 9 econdary /uantum num"er +hich
divide the or"ital in a hell into
maller group called su)shells,
Allo+ed value' from % to 4n Q $5,
m
l
9 magnetic /uantum num"er +hich
divide the u"hell into individual
or"ital, Allo+ed value' integer from
Ql to Rl,
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1elationships etween n, l, and m
l
.
2umer of
n l m
l
,ushell *ritals

1 0 0 1s 1
2 0 0 2s 1
1 31, 0, 1 2p 3
3 0 0 3s 1
1 31, 0, 1 3p 3
2 32, 31, 0, 1, 2 3d 4
5 0 0 5s 1
1 31, 0, 1 5p 3
2 32, 31, 0, 1, 2 5d 4
3 33, 32, 31, 0, 1, 2, 3 5f 7
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The appro)imate energie of the u"hell


in an atom +ith more than one electron'

Electron "ehave li2e tiny magnet


'he %uantum
numers
associated with
the first two
shells are
shown.
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Electron +ithin atom interact +ith a


magnet field in one of t+o +ay'

Electron pin i important in determining


electronic tructure
Electrons can spin in either
direction in the presence of an
e$ternal magnetic field. 'his
gives rise to the spin %uantum
numer, m
s
with allowed
values of 6102 !spin 7up8" or 9
102 !spin 7down8".
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According to the "auli e*clusion principle


no two electrons in the same atom can have
identical values for all four quantum
numbers

Thu t+o electron can occupy the ame


or"ital only if they have oppoite pin and
are aid to "e paired

A u"tance +ith more pin in one direction


i aid to contain unpaired electron
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Su"tance +ith unpaired electron are


lightly attracted to a magnet and are called
paramagnetic

Su"tance in +hich all electron are paired


are called diamagnetic

The ditri"ution of electron among the


or"ital of an atom i called the electronic
structure or electronic configuration
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To indicate the ground tate electron


configuration +e can'
$5 8it the u"hell that contain electron and
indicate their electron population +ith a
upercript,
>5 Repreent each or"ital +ith a circle and ue
arro+ to indicate the pin of each electron,

Electron configuration mut "e conitent


+ith the #auli principle* auf"au principle*
and Hund1 rule
E)ample' ( $s
>
>s
>
>p
E
* (a $s
>
>s
>
>p
K
Es
$
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Electron configuration e)plain the


tructure of the periodic ta"le
'he periodic tale is
divided into regions
of 2, :, 10, and 15
columns which is
the ma$imum
numer of electrons
in s, p, d, and f
sulevels.
,ushells that fill
across the periods.
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Ior the repreentative element 4A Group5


the electron +ith the highet n value or
valence shell are normally the only
electron important for chemical propertie

Ior thee element the valence electrons


consist of just the s and p subshells
encountered crossing the period that
contains the element in question
E)ample' the valence configuration of
"romine i
-r As
>
Ap
B

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There are fe+ important e)ception to the


.e)pected7 electronic figuration of
commonly encountered element

Iollo+ing the rule for Cr* Cu* Ag* and Au


uing no"le ga notation'
$ $% > ?
$ $% > ?
$ $% > ?
$ B > A
K SHeTB K SHeTB Cu
B SUrTA B SUrTA Ag
A SArTE A SArTE Cu
A SArTE A SArTE Cr
al E)periment E)pected Element
s d s d
s d s d
s d s d
s d s d
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Apparently* half:filled and filled u"hell


are particularly ta"le

Similar irregularitie occur among the


lanthanide and actinide element

The poition of an electron mut "e


decri"ed +ith pro"a"ilitie

Heien"erg1 uncertainty principle ay


that it i impoi"le to meaure +ith
complete preciion the velocity and
poition of a particle imultaneouly
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Thee limitation are not important for large


o"3ect "ut are very important for mall
particle li2e electron

Quantum mechanic re/uire that +e tal2


a"out the pro"a"ility of finding an electron
in a particular region of pace

Thi pro"a"ility i often repreented a an


electron cloud a"out the nucleu

The pro"a"ility varie +ith ditance from


the nucleu
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Thi type of plot ho+ that electron


density varie from place to place

Electron denity variation define the hape*


i6e* and orientation of or"ital
!a" - dot3density
diagram for an
electron in a 1s
orital. !" ;raph
of proaility
versus distance.
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p or"ital are /uite different from s or"ital

They poe a nodial plane +hich include


the nucleu and eparate the .lo"e7 of
high pro"a"ility
*ritals get larger as the
principle %uantum numer n
increases. 2odes, or regions
of (ero electron density,
appear eginning with the 2s
orital.
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Recall that there are three different or"ital


in each p u"hell
/ot3density diagrams of
the cross section of the
proaility distriution of a
single !a" 2p and !" 3p
orital showing the nodal
plane.
'he directions of ma$imum electron
density lie along lines that are
mutually perpendicular. It is
convenient to lael the oritals as p
$
,
p
y
, and p
(
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The hape and orientation of d or"ital are


more complicated than for p or"ital
Shape and directional propertie of the
five d or"ital in a d u"hell,

The f or"ital are even more comple) than


the d or"ital
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The amount of poitive charge .felt7 "y


outer electron in atom other than
hydrogen i called the effective nuclear
charge

Dt i lo+er than the atomic num"er "ecaue


of shielding
If the 23 charge of the
1s
2
core of lithium were
100< effective at
shielding the 2s electron
from the nucleus, the
valence electron would
7see8 a charge of 61.
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The effective nuclear charge felt "y outer


electron i determined primarily "y the
difference "et+een the charge on the
nucleu and the charge on the core

Effective nuclear charge control a num"er


of propertie

Atomic i6e increae top to "ottom in a group


"ecaue of increaing n and get maller left to
right in a group "ecaue the effective nuclear
charge increae
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Variation in atomic and ionic radii, Value


in picometer 4$%
:$>
m5
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The i6e trend in ion can "e ummari6ed'

#oitive ion are al+ay maller than the atom


they are formed

(egative ion al+ay larger than the atom


from +hich they are formed
-dding electrons leads to
an increase in si(e of a
particle, as illustrated for
fluorine. 1emoving electrons
decreases the si(e of the
particle, as shown for
lithium and iron.
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+oni'ation energy 4DE5 i the energy


re/uired to remove an electron from an
iolated* gaeou atom

Succeive ioni6ation are poi"le until no


electron remain

The trend in DE are the oppoite of the


trend in atomic i6e
+
+ e g $ g $ 5 4 5 4
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=ariations in first
ioni(ation3energies.
Elements with the
largest ioni(ation
energies are in the
upper right of the
periodic tale. 'hose
with the smallest
ioni(ation energy are
at the lower left.
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=ariations in
successive
ioni(ation
energies. 2ote
that it is
e$tremely
difficult to rea+
into the nole
gas core !2
nd

through >
th

ioni(ations for #i
through ?,
respectfully.
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The electron affinity 4EA5 i the potential


energy change aociated +ith the addition
of an electron to a gaeou atom or ion in it
ground tate

The addition of one electron to a neutral


atom i e)othermic for nearly all atom

The addition of more electron re/uire


energy
5 4 5 4 g $ e g $

+
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Conider the addition of electron to


o)ygen'

The reult for firt electron affinitie can


"e generali6ed
: :
: : >:
: >:
Change EA42JCmol5
!4g5 e ! 4 5 :$A$
! 4g5 e ! 4 5 8AA
(et' !4g5 >e ! 4 5 @%E
g
g
g
+
+ +
+ +
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Dn general'

EA increae from left to right in a period

EA increae "ottom to top in a group


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Meauring atomic mae
Meauring atomic mae
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