UNI

T-I
V

Magnet
o-Chemi
str
y

Magnet i
cI nduct ion:Whenaspeci menoft hemagnet i
cmat eri
alispl acedi na
magnet i
singf i
eld,magnet ism isinducedi nthespeci men.Thi sphenomenoni scall
ed
magnet i
ci nduction.Theendoft hespeci ment hroughwhi cht hemagnet iclinesof
for
ceent erbecomest hesout hpol eandt heendf rom whi cht heselinesl eavethe
specimenbecomet henor thpole.I tisalsodef i
neast het otalnumberofmagnet i
c
l
inesoff orcecr ossingt heuni tar ea(whichi sperpendiculartot hedi rectionoft he
magnet i
singlinesofi nducti
on)ar oundapoi ntlocatedwithint hespeci menpl acein
themagnet i
singf i
eld.Itisalsoter medasmagnet i
cf l
uxdensi ty.Themagnet icli
nes
ofinducti
onatanypoi ntwi t
hinthespeci menmaybemor eorl esst hant hemagnet i
c
l
inesofinduct ionatt hesamepoi ntofi ti
sint heairorvacuum.

Permeabil
it
y: I
tisdefi
nedast herat
ioofmagneti
cfluxdensit
yatanypoi
nti
nthe
speci
menoft hestrengthofthemagneti
cfi
eldappli
ed.IfBisthemagnet
icf
lux
densi
tyandHi sthestrengt
hoft hemagnet
icfi
eldappli
ed.Then,

Per
meabi
l
ity=B/
H

I
ntensi
tyofMagnet i
sat
ion(I
): Itr
epresent
st heext
enttowhichaspecimenget
magneti
sed when keptin magnet
isi
ng fi
eld.Quant
it
ati
vel
yitis def
ined as t
he
magneti
cmomentperuni tv
olume,i
.e.
,

I=M/
V

whereM,themagnet
icmomentgiv
enbytheproductoft
hepol
est
rengt
handt
he
di
stancebet
weent
hemagnet
icpol
eoft
hespeci
men.

Magneti
cSuscept
ibi
li
ty(K):I
tist
herati
ooft
hei
ntensi
tyofthemagnet
isat
ionoft
he
speci
menofthemateri
alandthest
rengt
hoft
hemagneticf
ieldappl
i
ed.

K=I
/H

I
tmeasureshow easi
lythemagneti
cthespecimencanbemagnet ised.Si
nceIis
magnet
icmomentperunitvol
ume,Kwouldbeexpressedasperuni
tvolume.Thati
s
whyKisalsoknownasvolumemagneti
csuscept
ibi
li
ty.

Li
kewise,gr
am magnet
icsuscept
ibi
l
ityχg,
ismagnet
icsuscept
ibi
l
itypergr
am oft
he
mater
ial.

Thus, χg=K/
d

Wher
edi
sthedensi
tyoft
hemat
eri
al.
Molarmagnet
ic suscept
ibi
li
ty χ,i
s magnet
ic suscept
ibi
l
ity permol
e oft
he
subst
ance.

χ=χgxM

=KM/
d

Or
igi
nofmagnet
icmoment

Theori
ginofmagneticmomentliesi
nthemot i
onofitsnegati
vel
ychargedel
ectrons.
Theoveral
lmagneti
cmomentofanat om istheresult
antofthemagneticmoment
gener
atedbytheor
bitalmot
ionofelect
rons,
call
edorbital
magneticmoment(μƖ)and
themagneti
cmomentgener at
edbyt hespinmot i
onoft heel
ectr
ons,cal
l
edspi n
magneti
cmoment( μs).

Orbit
alMagneti
cMoment( μƖ):Anegat i
vel
ychargedel ectr
onmov i
nginaci r
cul
ar
orbi
tissimil
art
ot heflowofel ect
riccurr
entinacircularwire.Theel ect
ronmot i
on
generat
esamagnet i
cf i
eldi nadi r
ecti
onperpendi
culart ot hepl aneoft heorbit
contai
ningt
heelectr
on.Themomentoft heelect
ri
cfieldsogener at
edisgivenbythe
productoft
heel
ectriccurr
entandt hesurf
aceareaoftheor bi
t .Thus,
2
Or
bit
almagnet
icmoment=μƖ=i
A=(
eω/
2πc)
πr …(
1)

Whererist
heradi
usoftheorbi
t,ωist
heangul
arv
eloci
tyofel
ect
ron,
cisv
eloci
tyof
l
ightandei
stheel
ect
ronicchar
ge.

Anelect
ronmovi
nginanorbitgenerat
esorbi
talangul
armoment
um (
Ɩ)whi
chi
s
per
pendi
cul
art
othepl
aneoft
heorbitandisgi
venby

(
Ɩ (
)= Ɩ+1)h/
Ɩ 2π ….
(2)

Sinceorbi
talangul
armoment um ofapar
ti
cleofamassm mov
ingi
naci
rcl
eof
2
radiusri
sgivenbymωr, hence
2
(
Ɩ)=mωr (
=Ɩ+1)h/
Ɩ 2π …(
3)
2
ωr (
=Ɩ+1)h/
Ɩ 2πm ….
(4)

Subst
it
uti
ngt
heabov
eequat
ion(
4)i
nequat
ion(
1),
wehav
e

Or
bit
almagnet
icmoment
,μƖ=(
e/ (
2c) Ɩ+1)h/
Ɩ (
2πm= Ɩ+1)
Ɩ (4πemc
h
)= Ɩ(Ɩ+1)B.M
Themagneti
cmomentμƖi
smeasur
edi
n uni
tsofBohrmagnet
on(
B.M)whi
chi
s
equal
to ( )
eh
4πmc

BothμƖand(Ɩ
)arevectorquanti
ti
es.Thesearecol
l
inearbuti
nopposi
tedi
rect
ions
andareper
pendi
cul
artotheplaneoftheorbi
t.
Exampl
e:cal
cul
atet
heor
bit
almagnet
icmomentofsandpor
bit
al.

Sol
uti
on:
Ɩ=azi
mut
hal
quant
um numberofor
bit
al

Fors-
orbi
tal (
s=0,
p=1,
d=2,
f=3)

Ɩ=0

(
μƖ= Ɩ+1)B.
Ɩ M

μƖ= 0(
0+1)B.
M =0

Ther
efor
eor
bit
almagnet
icmomentf
orsor
bit
ali
s0

SpinMagnet icMoment( μs)

:I
n1926Uhl enbackandGoudsmi tobser vedthatmov i
ng
elect
ronpossessesangul armoment um i nexcessofor bit
alangul armoment um.
Theyascribedt heexcessangularmoment um t
othespinningoft heel ectr
onaround
i
tsownaxi s.Thenegat ivel
ychargedel ectr
oninit
sspi nmot ionwi llalsoproduce
magnet i
cfiel
dwhosemomenti sdi
rectedalongthespi
naxi s.Theyal sopostulated
thattherati
oofspi nmagnet icmomentt othespi
nangularmoment um ist wi
cet he
rati
oofμƖt o(Ɩ)int
heirrespecti
veunit
sofB. M.andh/2π.Ther ati
oofspi nmagnet i
c
momentt ospi nangularmoment um i
scal l
edLandespli
tti
ngf actor,g.thus,

μs/
(s)=μs/s(
s+1)=g

μs=g s(
s+1)=2 s(
s+1)B.
M.

t
heaboveequati
onisspi
nonlyformulaf
ormagneti
cmoment.Byr
ecogni
singt
hats
wi
ll
berel
atedtothenumberofunpai
redel
ect
rons(
n)bys=n/
2

( = n(
μs) n+2)B.
M.Wher
en=numberofunpai
redel
ect
ronspr
esenti
nanat
om ori
on

Theabov
efor
mul
aisnotappl
i
cabl
einf
-bl
ockel
ement
s

##Int ransit
ionmetalions,theunpair
edel ectr
onsar egener al
lypresentintheouter
orbi
tals.Theor bi
talsmot i
onofunpai redel ectronsorf reemet alionsi ssever
ely
di
sturbed by t he presence ofl i
gands t hereby quenchi ng t
he or bit
alangular
moment um inthetransiti
onmet alcompounds.Ther efore,i
nsuchcases,t he μs
contr
ibut i
onbecomemor eandmor esi gnifi
cantt hant heμƖ contributi
on.SoμƖ
contr
ibut i
onmaybenegl ectedi
naf ir
stt r
ansitionseries.Themagnet icmoment (μ)
i
nsuchcasesmaybegi venbytheexpr ession

μ=μs= n(
n+2)B.
M.

Di
amagnet i
sm :Thesubst
ancewhi
chwhenplacedinamagneti
cfi
elddecr
easedthe
i
ntensi
tyofthemagneti
cfi
eldt
hani
nvacuum arecal
leddi
amagnet
icsubst
ance.

Asubstanceinwhichoneormoreorbit
alscontai
npai
redofelect
rons,t
hetwopaired
el
ect
rons resi
ding i
nt he same or
bit
als hav
e opposi
te spi
n,the spin magneti
c
momentofone el ectron wil
lbe equaland opposi t
et ot hatofot herel
ectr
on
occupyi
ngthesameor bit
al.Thi
swi l
lresul
tinthemagnet icmomentofoneel ectr
on
wil
lbecancel
ledbyt heotherelectr
onr esi
dinginthesameor bitalandconsequentl
y,
i
fsuchsubstanceisplacedi nthemagnet i
cf i
eld,
itexperi
encesr epul
sionandhence
showsdiamagneti
cbehav i
our.Diamagneticsubstancepermitslessnumberofl i
nes
offor
cetopassthroughi t.

Di
amagnet
ism i
st emperat
urei
ndependent
.Sincei ndiamagneti
csubst ances,t
he
magnet
icf
iel
dinducedisinthedir
ecti
onwhichi soppositetothedirect
ionofthe
magnet
icf
iel
dappl
ied,di
amagnet
icsuscept
ibi
l
ityχdiai
salwaysnegat
ive.

Paramagnetism:Subst
ancewhicharef r
eel
ymagneti
sedi
nt hedirect
ionoft he
magneti
singf i
eldi
nwhi
chtheyarepl
acedandwhenpl
acedi
nthemagneticfiel
dthe
i
ntensi
tyofthemagneti
cfi
eldar
eincr
easedarecal
l
edpar
amagnet
icsubstance.

Systemscontai
ningoneormor eunpair
edel ectr
onshaveaper manentmagnet i
c
moment ,i
.e.
,the indi
vi
dualatomsormol eculesofsuch substance behav
e as
permanentmagnets.Thi
sisbecauseal
lthemagnet icmoment
sofel ect
ronsinthese
atomsormolecul
esdonotcancel oneanother
.

When a par amagnet ic substance is pl

aced i
nt he externalmagnet i
cf ield,the
i
ndivi
dualatomsormol eculesbehavingpermanentmagnet salignthemselvesi nthe
samedi rect
ionast hatofext er
nalfi
eldandarethusat tractedtowardsthefield.Asa
resul
t,thepar amagnet i
csubst ancesal l
ow alargernumberofmagnet icl i
nesof
i
nduction to pass t hrough them t han thr
ough ai r
.Magnet i
c suscepti
bilit
y of
paramagneticχparawouldbeposi ti
ve.Iti
stemperaturedependent .

Fi
g.magneti
cfi
eldl
ineswhenadi
amagnet
icandpar
amagnet
icsubst
ancepl
acedi
n
anext
ernal
magneti
cf i
eld

Ferromagnet i
sm:When a par amagnet
ic substance ar e placed in an ext er
nal
magnet icfi
eld,t he magneti
cmomentar e al i
gned withr espectt ot he exter
nal
magnet icf
ield.Incaseoff er
romagnet i
csubst ances,thealignmentoft hemagnet i
c
moment sdoesnotunder go anychange,ev enift heext ernalmagnet icfieldis
remov ed,i.e.,unli
ke the par amagneti
c subst ances,t hese substances exhi bi
t
permanentmagnet ism evenaftert hemagneticf i
eldisremov ed.Suchsubst ances
are call
ed ferromagneticsubst ances.In case off err
omagnet i
csubst ances the
ali
gnmentofal lmagneticmoment sisint hesamedi recti
on and hencesome
subst
anceshav
edefi
niteval
ueofthei
rmagneti
cmoment.Thusaf er
romagneti
c
subst
ancecanbedefinedasthatsubstancei
nwhi
chthealignmentofallthe
magneti
cmomentsi
sinthesamedi
rect
ion.

Anti
-f
err
omagnet i
sm :I tisthesubst ancei nwhicht henumberoft hemagnetic
momentv ectorsalignedinonedi rect
ioni sequaltot henumberoft hemagnetic
momentv ector
salignedinopposit
edi r
ect i
onandhencesuchasubst ancehavezero
val
ueforitsresul
tantmagneticmoment .Inotherwordswecansayt hatt
hehalfof
t
hemagnet i
cmomentv ect
orsalignedi nonedi rect
ionwhi l
et heremaini
nghalf
magneti
cmomentv ect
orsar
ealignedint heopposi
tedirect
ions.

Fi
g.al
i
gnmentofel
ect
ronspi
ns

Cur
ie’
sLaw:

I
n 1895 Pi er
re curie est
abl
ished t
hatpar amagneti
c susceptibil
i
tyisinv ersely
proport
ionaltot he absol
utetemperature.In ot
herwor d we can sayt hatt he
magnet i
c suscepti
bil
it
y ofthe paramagnetic subst
ance,χpara wouldther efore
decrease wit
hi ncrease i
nt emperature.Theref
oret he var
iation ofχpara with
temperaturei
sexpressedas

χpara=C/
T

theabov
eexpressi
oni
sknownasCur
ie’
slaw.Wher
eC i
saconst
antknownas
Curi
e’
sconst
ant
.

Thecurie’
slawisobeyedfai
rl
ywel
lbypar
amagneti
csubst
ancethatar
emagneti
call
y
di
lutei.
e.,thosei
nwhi chthepar
amagnet
iccent
resarewellsepar
atedf
rom each
otherbydiamagnet
icatoms.
Cur
ie’
s-Wei
ssLaw:(
modi
fi
edf
orm ofCur
ie’
slaw)

Inmater
ial
sthatar
enotmagnetical
l
ydil
ute,unpai
redspi
nsonneighbouratomsmay
coupl
e wit
h each ot
her,a phenomenon r ef
err
ed to as a magneti
c exchange.
Mater
ial
sthatshowexchangebehavi
ourcanusuall
ybetreat
edbyCurie’
s-WeissLaw.

χpara=C/
(T‒θ)

wher
eθi
sknownasWei
ssconst
ant
.Theabov
eequat
ioni
sCur
ie’
s-Wei
ssLaw.

Var
iat
ionofmagnet
icsuscept
ibi
li
tywi
tht
emper
atur
e:

I
nanymat eri
alt
hatexhi
bitmagneticex change,t
hetendencyt owardsspinali
gnment
wil
lcompletewi
ththethermaltendencyf avour
ingspinr andomness.Insomecases
t
herewillbesomet emperatur
ebel ow whi chmagneticexchangedomi nates.Thi
s
t
emperatureiscal
ledCurietemper ature(Tc)ifthetypeofexchangedi splay
edis
f
erromagneti
candtheneeltemper ature(TN)i
fiti
santiferromagneti
c.Thechangeis
l
ikel
yasthetemperat
ureisdecreasedbel oweit
herTcorTN maybequi t
edramat i
c.

Fi
g.v
ari
ati
onofmagnet
icsuscept
ibi
l
ity
(χ)wi
tht
emper
atur
e.

1.Incaseofpar amagneti
csubst ance,duet othermalagit
ati
ont
heatomicor
molecul
armagneticdipoleswhi chgetal i
gninthedir
ecti
onofthemagnet
ic
fi
eld appl
ied wouldt end to al i
gn randomly.Therefor
ethe magnet
ic
suscept
ibi
l
itydecr
easeswi t
hincr easei
nt emper
atur
e.

2.Inaf erromagneti
csubst ancet hef err
omagnet icbehaviourofasubst ance
exi
stsupt oapar t
iculartemper at
ureknownasCur ietemperatur
eorCur i
e
poi
nt( Tc).Abovethist emper at
uret het endencyofmagnet icmoment sof
domainst oal i
gnint hepr esenceofmagnet i
cfiel
disopposedbyt hermal
agi
tat
ion whi ch t
ends t or andomise t he magnetic moment s and star
ts
 behavi
ngasanormalpar
amagneti
csubst
ance.Themagnet
icsuscept
ibi
l
ity(
χ)
foraferr
omagnet
icsubst
anceismuchhigherthananormalparamagneti
c
subst
ance.

3.Forant i
fer
romagneti
csubst anceal
so,ther
ei sachar act
eri
sti
ctemper at
ure
known as neel t emperature or neel point (
TN), above whi ch the
anti
ferr
omagneticsubstancebehaveasnormalparamagnet i
csubstance.But
,
bel
ow t he neeltemper at
ure magneti
c suscepti
bil
i
ty( χ)decreases with
decreaseintemperatur
e.

Abovet heTN,noelectronspinpairint
eracti
onsarepossibleandonl ythe
uncoupledandcompl et
elyrandomisetotalel
ectr
onspi nsofatomsori ons
exi
st.Thereforeattemperatur
eabov etheTN antif
erromagnet
icsubstance
behaveaspar amagneti
csubstanceandχi salsodecreasedwit
hincreasein
temperatur
e.

Belowt heTN,thethermalener
gyav ai
l
abletoant i
fer
romagnet i
csystem isless
thantheener gyofelect
ronspinpairi
nteract
ions.Aswegoondecr easingthe
temperature,theuncoupli
ngandrandomi sat
ionoftot alel
ectr
onspi ngoeson
decreasingandχal sodecreasestheextentofcouplingoft ot
alelectr
ongoes
onincreasing.Theref
oreχdecreaseswithdecreaseint emperatur
e.

TheMagnet
icbehav
iourofsi
mpl
einor
gani
ccompl
ex.Expl
ain
4-
1.
[Mn(
CN)
6]

2+
2..
[Mn(
H2O)
6]

3.K3[
Co(
CN)
6]

4.K3[
FeF6]
4-
5.[
Fe(
CN)
6]

3-
6.[
CoF6]

Bohrmagnet
on(
B.M.
):

Bohrmagnet
oni
susedf
ort
heexpr
essi
onofmagnet
icmoment
.Iti
sgi
venbyt
he
expr
essi
on

B.
M.= (4πemc
h
)
ehi
Wher splanck’
sconst ,ei
ant stheel
ect
roni ge,ci
cchar sthev
eloci
tyofl
i
ghtand
misthemassofel
ectr
on.