RelationbetweenColor and

constitution

Electro magnetic radiation

Lightiselectromagneticradiation(thatis,ithasbothelectricalandmagneticcomponents)vibratingin
transversewavepackets,orquanta.
Thevibrationmayoccurinallplanesorinoneonly(planepolarizedlight),eachplanehavingrightand
leftcircularvectorcomponents.Wemaymeasuretheamplitudeofthewavequantum(intensityof
thelight),i tsfrequency,u,and/orwavelength,X(color ortone),andi tsvelocityinagiven
medium,v.

Color, Chromophore and Auxochromes

Thecarbonylandethylene(vinyl)groupshavechromo phoric propertiesonlywhentheyarepresent
inthemoleculeinmultipleconjugatedorder.Thus,acetoneiscolorless,whilediacetyl isyellow,asis
benzil whichisdeeperyellow,andtriketopentane isyelloworange.Sincei tisthedelocalizationof
pielectronsthatisrelatedtotheproductionofcolor,i tisevidentfromtheseexamplesthat
suchdelocalizationaccompaniesmultipleconjugatedunsaturation.

Chromophores

O.N.Wittobservedin1876thatcoloured compoundscontaincertainunsaturatedgroupswhichhe
calledchromophores andcompoundcontainingachromophore iscalledachromogen.Whencertain
groupscalledauxochrome arepresentinthechromogen adyeisobtained.

Q u in o n o id

N itro s o

K e to

O
C

N
O

\E th y le n ic

N itro

C h ro m o p h o re s

A zo

Auxochromes
Auxochrome maybeeitheracidicorbasiclikeOHorNH2.Otherauxochromes includeCOOH,SO3H,
NR2 thesegroupsformsaltswitheitheracidsoralkalies.theyalsoformhydrogenbondswithcertain
groups(OHofcelluloseorNH2 ofwool,silk).

(A zo b e n ze n e )
c o n ta in in g -N = N - c h ro m o p h o re
N o t se rv in g a s d y e

(p -A m in o a z o b e n z e n e )
-N H

a u x o c h ro m e

A d isp e rse d y e

NH

CLASSIFICATION BASED ON CHEMICAL NATURE

Indigoiddyes: Thisisthemostimportantgroupofnaturaldyes.Thedyestuffisextractedfrom
Indigofera tinctoria,abushpeafamily.ThedyewasusedprehistoricallyinIndia,whereitprobably
originated.ThewordisderivedfromIndican.

Anthraquinone dyes
Anthraquinone dyes: Someofthemostimportantreddyesarebasedontheanthraquinone structure.
Theyareobtainedbothfromplantsandinsects.Thesedyesarecharacterizedbygoodfastnesstolight.
Theyformcomplexeswithmetalsaltsandtheresultantmetalcomplexdyeshavegoodwashfastness.

Alpha-napthoquinones
Alphanapthoquinones: Themostprominentmemberofthisclassofdyesislawsone.Itisobtainedfrom
Lawsonia inermis

Flavones:
Flavones:Flavone iscolorlessorganiccompound.Mostofthenaturalyellowcolorsarehydroxy andmethoxy
derivativesofflavonesandisoflavones.Itisobtainedfromasdustonflowersandseedsofvarious
Primula species,inbudsofvariousvarietiesofpoplar,inyellowdahlias,inweld(Resedaluteola)and
dyersbroom(Genista tinctoria).

RELATION BETWEEN COLOR AND CONSTITUTION

Likethephysicalandchemicalpropertiesoforganiccompounds,thereisadefiniterelationshipbetween
thecolorandconstitutione.g.,Benzeneiscolorless,whereasitsisomer,fulvene iscolored.Thefollowing
theorieshavebeenproposedtoexplaintheobservedgeneralrelationshipsexistingbetweencolorand
constitutions

Wittstheory (ChromophoreAuxochrome theory): In1876Wittputforwardatheoryaccordingto

whichthecolorofasubstanceismainlyduetothepresenceofanunsaturatedgroupknownas
chromophores (Greekchroma color,andphores bearing).Theimportantchromophores are:
C=C
C=N
C=O
N=N
NO2
Quinoid rings

Thecompoundspossessingchromophores areknownaschromogens.Thechromopheric groups

areofthefollowingtwotypes.

Whenasinglechromophore issufficienttoimpartcolortothecompound.Examplesare:NO,
NO2,N=N,=N=NN,N=NO,pquinonoid etc.

Whenmorethanonechromophore isrequiredtoimpartthecolor,e.g.>C=O,>C=C<etc.Thiscan
beexemplifiedbyvariousexamples.Acetone(havingone>C=Oaschromophore)iscolorless,
whereasbiacetyl (withtwo>C=O)isyellow.

How does it work

Sincetheauxochromes arecapableofformingsaltseitherwithabasicoracidicgroupstheirpresence
alsoconvertacoloredcompound(devoidofsaltforminggroups)intoadyewhichmustfixpermanently
tothefiber,i.e.,itmustbefasttowater,light,soapandlaundering,whenfixedtothefiber.The
permanentfixingofdyetothefiberisgenerallyduetotheformationofchemicalbondbetweenthe
fiberandtheauxochrome.Thiscanbestbeexemplifiedbythefollowingexamples.

Benzene

Diazobenzene

Armstrong Theory (Quinonoid theory):

ArmstrongTheory(Quinonoid theory):Armstrongin1885suggestedthatallcoloringmattersmaybe
representedbyquinonoid structures(p oro),andthusbelievedthatifaparticularcompoundcanbe
formulatedinaquinonoid formitiscolored,otherwiseitiscolorless.Someoftheimportant
compounds,thecoloringpropertiesofwhichcanbeexplainedonthebasisofthistheoryaregiven
below.

Onthebasisofthistheorywecanseethatbenzeneiscolorless,whereasbenzoquinones arecolored.

Butthequinonoid theoryisnotsufficienttoaccountforthecoloringcharacteristicsofallthe
compounds.Forexample,iminoquinone anddiiminoquinone,bothpossesaquinoid structureeven
thentheyarecolorless.

Benzene

Benzoquinones

Imnoquinone

Di-iminoquinone

Modern Theory

ModernTheory:Theabovetwotheorieswerediscussingtherelationshipbetweencolorand
constitutionarefoundtobeonlyempirical.Thenexttwoimportanttheories,whichexplain
plausiblytherelationbetweencolorandconstitution,requiresomewhattheoretical
backgroundabouttheeffectoflightonthemolecule.
Valencebondtheory
Molecularorbitaltheory

Valence bond theory

Valencebondtheory:Thevariouspostulatesofthistheoryareasfollows:
Chromophores aregroupsofatoms,theelectronsofwhichmaygettransferredfromground
statetoexcitedstatebytheabsorptionofradiation,thusproducingthecolor.
Auxochromes aregroups,whichtendtoincreaseresonancebyinteractingtheunsharedpairof
electronsonnitrogenoroxygenatomsoftheauxochromes withtheelectronsofthe
aromaticring.Thisincreaseinresonanceincreasestheintensityofabsorptionoflightandalso
shiftstheabsorptionbandtolongerwavelength.Hencethereoccursthedeepeningofthe
color.Fromthisitisevidentthatincreaseinresonancemustdeepenthecolorandactuallyit
hasbeenfoundtobeso.

Further More

Thedipolemomentchangesasaresultofoscillationofelectronpairs.Thefollowingorderhasbeen
observedforthecaseofexcitationofdifferentgroups.

N=O>C=S>N=N>C=O>C=N>C=C
Resonancetheoryexplainstherelationofthecolorandthesymmetryofthemoleculeortransition
dipoleofthemoleculebecauseasthenumberofchargedcanonicalstructuresincreases,thecolorof
thecompounddeepens.Themorethepossibilityandlongerthepathforachangetooscillateina
compound,thelongerwavelengthoflightwillbeabsorbedandthereforedeeperwouldbethecolor
ofthecompound.

Molecular orbital theory

Molecularorbitaltheory:Accordingtothistheorytheexcitationofamoleculemeansthetransferenceof
oneelectronfromanorbitaloflowerenergytothatofhigherenergy.Theseelectronsmaybe,orn
(nonbonding)electrons.Thehigherenergystatesarecommonlyknownasantibondingorbitals.The
antibondingorbitals associatedwithandbondsarecalled*and*orbitals respectively.However,
therearenoantibondingorbitals associatedwithn(nonbonding)electronsbecausetheydonotform
bonds.Chartofthesimplestform,theessentialtypesofenergyaregivenin thenextslide:

.
Chart showing molecular orbitals
*

Anti-bonding

Anti-bonding

Lone-pair Non-bonding

bonding

bonding

Electronic transitions

Theelectronictransitionscanoccurbytheabsorptionofultravioletandvisibleradiation.Although
transitionsarepossible,onlythefollowingtypesareallowed:
n*
n*and*

A*transi ontakesplacewhenabondingelectronisexcitedtoanantibonding orbital,i.e.

*.Thistypeoftransitionrequiresaverylargeamountofenergyaselectronsareverytightlybond.
Hencethecompoundslikesaturatedhydrocarbonswhichdonothaveanyorelectronsmayundergo
only*transi ons.However,thesetransi onsdonottakeplacebyabsorbingintheordinaryultra
violetregion,e.g.,ethaneabsorbsat135m.