Optical Propierties ofChiral Compounds

Chiral compounds hasthe same physical properties

(boiling point,melting point,density,etc.)with the
exception ofthe desviation ofthe polarized light
known asoptical rotation.

Lightiselectromagneticradiationthat
oscillatesperpendiculartoitsdirectionof
motion.
Theoscillationoflightcanberesolvedinto
twoperpendicularcomponents.
Whenlightispassedthroughapolarizer,
onlyoneofthetwoperpendicular
componentsoflightispassedthrough.This
lightisreferredtoasplanepolarizedlight.
Plane polarized light
 Enantiomerscannotbedistinguishedonthebasisoftheirphysical
properties,suchasboilingpoints,meltingpoints,anddensities.
Enantiomerscanbedistinguishedbythewaytheyinteractwithplane
polarizedlight.
Whenplanepolarizedlightispassedthroughasampleofoneofthe
enantiomers,theplaneofpolarizationisrotatedeitherclockwiseor
counterclockwise.Whentheexperimentisrepeatedwiththeother
enantiomer,theplanepolarizedlightisrotatedanequalamount,butin
theoppositedirection.
Iffacingthelightsource:
Clockwiserotation:enantiomerisdextrorotary(+)
Counterclockwiserotation:enantiomerislevorotary ()
Thisinteractionwithlightiscalledopticalactivityandenantiomersare
oftencalledopticalisomers.
 DiagramofaPolarimeter

Themeasuredrotation(indegrees)istheobservedopticalrotation,,ofthesample.
Thevalueof dependsupon:
Structureofthechiralmolecule
Concentrationofthechiralmolecule
Lengthofthesamplecell
Wavelengthofthelight
Solventused
Temperature.
 Thespecificrotation[]ofasampleisdefinedforeachchiral
molecule(thevalueissolventdependent):

[ ]t
o

l c
where [ ] = specific rotation
t = temperature in degrees Celsius
= wavelength of incident light
(D = 589 nm, the yellow D line from Na)
= observed optical rotation in degres
l = sample container length in dm
c = concentration (g/ml)

Enatiomers havethesamespecificrotationbutwithdifferent
signal.
Opticalrotationindicatesenantiomeric composition
Aracemicmixtureisamixtureofequalamountsofthe+and
enantiomersofachiralcompound.Itshowsnonetrotationofplane
polarizedlight.
Whenoneenantiomerequilibrateswithitsmirrorimage,theprocessis
calledracemization.
Whenoneofthetwoenantiomersofachiralcompoundispresentina
mixtureinexcessovertheothertherewillbeanetrotationofplane
polarizedlight.
A50%enantiomerexcesswouldbedefinedasamixtureof75%one
enantiomerand25%oftheother[50%(+)with25%(+)and25%()].The
mixturewouldbecalled50%opticallypure.
Theopticalpurityofanenantiomerisdefined:
observed
% optical purity 100 enantiomer excess