.

( ,

U lt ra vi o le t Spectroscopy

TATION
3.1 BASIC CONCEPTS AND INSTRUMEN

3.1.1 Introduction ed when electrons

with the measurement of energy absorb
UJtraviolet absorption spectroscopy deals
are promoted to higher energy levels. the absorption
of wavelength of light absorbed versus
The ultraviolet spectrum is simply a plot absorptivity_
(abs orba nce or tran smi ttan ce) and is conveniently recorded by plotting molar ,
intensity tice from as low as 10 to as high as 100,000
gth (nm ). Sin ce e valu es rang e in prac
(i? against wavelen
it is convenient to use log £ as the abs
cissa of UV spectrum. ei
tain s elec tron ic, vibr atio nal and rota tional energy levels. Each electronic lev
A molecule con separations and
mt!er of vibrationaUevels with less energy
within a molecule, is associated with a _!!!! energy
nal leve l in turn is asso ciat ed with a set of rotational levels with eve n less
each vibratio
separations, as shown in the Fig. 3.1.

----
------ Vo

----
II Ea

Rotational {
--
-- Vl] Vibrational
levels
levels
--+-++;.._ VI

__,_~;.... Vo
----Vo

Fig. 3.1 Electronic ener&Y levels.

ation, they are
ly larg er amo unts of energy associated with the ultraviolet radi
Due to the rela tive
tran sitio ns in the electronic, vibrational and rota
tional
tron ic exc itati ons and indu ce
~D abl e of elec
IY levels of a molecule.
,.-:-
120 ORGANIC SPECTRoscoPY
Thus. the ultraviolet spectrum of a molecule results from transitions
levels ac:campanied by changes both in vibrational and rotational s1a1es.
between
. .
electronic
•
energ
y

s.. • ...
ULTRAVIOLET SPECTROSCOPY
The n orbitals Ii~ at s~mewhat h!gher energy and the orbitals holding the unshared elect~on p~irs
(non•bonding orbitals) lie at even _higher e~gy levels than the norbitals. The unoccupied or anttbondm_g

121
c_
orbitals (tr' and 0'4') are the orbitals of highest energy. A typical progression of the energy levels 1s
illustrated in the Fig. 3.3.
3.1.2 Th• Ultraviolet spectrum
The ultraviolet spectrum may be divided into the following regions:
'/
Antibonding e(:) (sp3 - sp3) \
(i) Far (or w,c11""') 11ltravioltt ( J0-200 nm).
n a• variable
The region from 10-200 nm canbe stuaied ,n evacuated systems and is termed as "vacuum ultraviolet". • ft"
............ (p-p)
The aunospheric absorptions below 200 nm is a blessing to all, including the spectroscopists, since I
it prevents die bazardouS (high energy) ultraviolet radiation in the sunlight from striking the earth's • nm (weak)
surface. In organic molecules. the maximum energy separation occurs when e..!~ in CT bonds arc T
~xcited giving rise to absorption in the ~g__e 120-200 nm. The range is difficult to measure and7s"'s f n
.. 180 nm (stron,~)......... (p) t
ollitde diagnostic-wlueif'ig-:D,.-- &3
\ d- _ ,_ • IC
....... A'•·•J '
.......
Flrarv.-m
(...nycacared

Near«
quartz
alnviolet

. Visible region
r' ..
(1

<1 <1• < 180 om (strong)

Bonding
or
(sp'-spltsp1-sgltsp-sp)

"
b , • • · lit'.
allimplims) ec:::::o (sp'-stsp2-slsp-s)
10- 200nm 380nm 780nm Fig. 3.3 Electronic energy levels and eledroaic tramitioas.
Fig. 3.2 tntraviolet-vislble spectroscopic regions. II 3.1.3.2 ELECTRONIC TRANSITIONS
(iii liar or Qw,tt% llltraviolet (2~380 nm) . The electrons in organic molecules may be involved in bonding as strong a bonds. weak 1tbonds or
lk aap from 200-380 nm is the portion of the spectrum normally covered by the term ultrav1olct. present in the non-bonding form (lone pair). A variety of energy absorptions for electronic transitions
-ne t r ~ ls transparent in this region and quartz optics may be used to scan from 200-380 nm. within a molecule.is tlius possible depending upon the nature of bonding. Absorption of ultraviolet
'lleeie~'>f clecbOUi fromp & d orbitals, ,r-orbitals and particularly ,rconjugated systems radiation. therefore. elevates these different types of electrons to excited antibonding orbitals as
.._.acwemd .:-gives rise to ~ l y accessible and info~ative spectra. shown diagrammatically in the Fig. 3.3.
The wavelength of UV radiation causing an electronic transition depends on the energy both of the
_,_(~780nm) . orbitaJ originat"ly occupied by the electron and of the higher energy orbital (generally antibonding) to
- . wbicb is accessible with most instruments is from 200 n111 to 800 nm and this which it is promoted.
. . -ii often refe.n:d to as ultraviolet spectrum although it includes the visible region (380
• - ~ tunptat fil1rna1t lamp is generally used for the visible region of the s~trum. Types of e(ectronic transitions
"'9 If V•• of double bonds lowers the energy ~uired for the transition and absorption moves important modes of electronic transitions when a molecule absorbs radiation in ultraviolet or
. .. . , . , Wbea there are enough double b o ~ r p t i o n will move into v1s1ble region arc described below: •
·--
,,,,..._ ffliaa and the compound will be coloured. ~arotene, for example, contains eleven
II-Cllbo.a double bonds in conjugation and owes its colour to absorption in the visible region of Transitions between bonding and antibonding orbitals
~•451 DID). Transitions between bonding and anitbonding orbitals arc illustrated in Fig. 3.4. They arc of two .- I
types:
Ba~• Wt'IJ levels, electronk transitions and selection rules C14' (bonding a to antibonding o).
J.J.3.1 Bl.ecraOlac f.NEIGY lEVELs (u) tr tr' (bonding ,r to aritibonding n).
al ldtraviolct racH•tion by an • • • ( i) a 0- transition ( J20-20() nm)
. . . , ,..., Inda widun the molecule 1ecule
leads to electronic excitation ,mong The excitation between bonding sigma and antibonding sigma orbitals <r- transition) requires
~orlJit.laaclmllM Ccupicdnon~!™•~ ona ~ l y occur in between~ bonding~ large energies corresponding to absorptions in the far ultraviolet region in the range from 120-200
levels, in 11101t orpnic.ino•~..::.:~ital. Tbecnergy difference between nm. Thus, these transitions in saturated hydrocarbons. containing just a bonds. remain transparent in
Tbe t1,w1,,;~·•· • 1 .- • -.uaca, vana from 30 to 150 a......, J the near ultravilet/ or visible region. For example. methane. propane. cyclohexane etc., display
• aavo """ ~ J t1bonda1.are the low ~IJJO ~. ·
• ·-- --~ OCCUp1ed molecular orbitals, transitions and A.m.x for each of these compounds is below 140 run.
 --.......
.......------ ------ ----
-
-
SreCTRoscorv-
-y~
OR0ANIC ULTRAVfOl_,eT SP2CTROSCOPY 123
122
OY n (non-bonding atomic orbital to antibonding 1(J
oc•CC. @~4 (W' 11 a- (non-bonding atomic orbital to antibonding dJ ·
(I}"~ n•
~(J Transitions between non-bonding atomic orbitals holding un~harcd pair of electrons and antibonding
pi-orbitals arc called n tr- transitions. Non-bonding electrons arc held more loosely than u
ceca (a) <J -+0- Transition bonding electrons and consequcntfy undergo transitions at comparatively longer wavelengths. These
transitions ~_£~r with ~o~po~nds containing d_?u~le bQnds involving hetero-_atgms f?earing unshar~
=
c,~•No
.,, J ',,
n aCN
\ .
=
&'air(gfo,-clcctrons "(e.g., C O; C find' N O etc.). Thistype of transition is an important
feature of the spectra of aldchydcs and kctones and is sensitive to substitution on the chromophore
structure. For example, the spectra of aldchydes or kctoncs exhibit two bands; a more intense band
at 180-200 nm, corresponding to
transition at about 280 nm. •
transition and a low intensity (Jess probable) n .-+- ,,..
"-- .J
\c_No
/\ ~r,,.
00 n(sp')
9tf'~ ''
'
~) &,,,~ ::::- t->~-#_- ~---
'0 I r r ~ ~ .-,~~J

0
ac~ '7c;o
\_N_ 00
-;/ .
~ ' - :t:;::A. .l)
<1cN
_-;,..
,,7\,
.t-"··_,.
Q/.
(b) n -+ a-Transition
',,, 0
',,, ---,r-
~o .~ ---,r-
•
'c-c"'
~n-
',,~;;,, ..
~a
', , ',,
' \.,_,.I ... 00
'c---c' ----,r 'c-o n(P,)
"
(c) Ir-+ ,r- Transition
Fig. 3A FJectronic Transitions: (a) 0- Transition (b) n - ,,. Transition (c) _.Tramltion. .... ,,,---...
(ii) ,r
',
'c-o 1C
Transitions between bonding pi and antibonding pi arc called transitions...,These transitio~
,,
, occur with rompouAds co.ataining-eonventionaldQ_u-Elc or triple bonds. aromatic rings and carbonyl
.QC ll-0,lro'lps Although ethylene absorbs strongly around 180-nm-m the far UV region, conjugated
region. systems are more readily excited. Butadicnc (Amax= 2 I 7 nm) absorbs in the accessible
,relcctron UV ' ', ....---.... '
C oe ••
)~
s~•i-•1
~-~otar: absorptivity, for 7r ~_n-_transition is very high (Emu> 10000) because then and rff
•to are.'~
orbitals in~tanc
orbital IS very high. and corisequently1he-probability of the jump of an electron frorn ... , -,
..
;;c-•oC) •• n(sp)
000
-~ so obetf
~altion two types: -bondlng atomic orlbitals and antlbondlna orbitals
ween
., Fi&. 3.5 1f _. and ,. r Transitions of the Carboa.,vl Group.
~.:.
124 ORGANIC SPE(."'l'R
()SCOPY
. nse t,ccau-
. . . always tess ante

. then-orbital are situated ~rpend~ular

·• the electrons ,n. I) nd consequ ently the probabi) lty
- orb1ta
e lane of the ". a
. fact zero accord'mg to symmetry
-J .1.4 Th• origin, gen~ral appearance and designation of UV bands
ULTRAVIOLET SPECTRO SCOPY 125
n-+~Tra ns1non; ~ (and tiertee to t:b~tal is very tow_ and in ut a partial (a) The ~rig in and g_eneral appea~~nce of bands
overlap between the
to the pl•~~ff. ~ etecifon fr<>"' " to-~ations of atoms bnns . .
of the Jump o •~ 3 6. However, v1 r . . does occur, but a~ to a limited extent. Electron ic ~pectra arise f~om trans1t1on_s between electronic energy levels
on y • accompanied by change~ m
selection rules Fig, •nd so n -+ tc"' 1rans1uon t,oth vibrational and rotational. states. Since the wavelength of absorptio n is a measure of the separatio n
perpendicular p1ancs • , • I of the energy l~vels ~f the orbitals concerned, a transition between these
levels, when gaseou.s sample
15 irradiate d, gives rise to fine structure consisting of a number of closely spaced lines which, very
I r-a~·
"-?· oo
~., ,I
....,::.:..+ ~c
cl~oo
Y
4
•
•
O ;
0
•
0 ften, merge (due to solvent-solute interaction) to give a broad absorption band,
casurem ents are carried out in solution.
when spectral
.,_-- - y.,. "·Jt-"'I .· m Electron ic absorpti on bands arc, therefore, usually broad as compare
d to infrared or NMR bands.
- Excitation or the carbonyl group. (b) Designa~ ion of UV_band s
fig. 3.6 " 11,~
•
The absorpti on bands m the UV spectrum may be designated either
by using electronic transitio ns
(3.1.3.2) or the letter designation•, as illustrated below:
(ii} 11 a-, rronsition • . nshared air (non-bonding electrons) on nitrogen, oxygen,
11le excitation of an electron in an u .
or halogens to an antibonding a orb1ta1 is ca
lied a- transition. Examples of molecules (I) R-Band s (German, radikalartig)
n .
sulph~ bso t'on because of n a- transitions are as follows: The bands attribute d to transition s of
sllc,wing a 'P I single chromop horic groups, such as the carbony l or
t-ti ·
183 (£ =500) nitro group, are referred to as the R-bands (German . radikalar tig). They arc characte rized by low
( t4cthang! ~) Amax= nm (£ =486) molar absorpti vitics (Emax < 100) and undergo hypsochromic shift with
Amax~ . .257 nm . an increase in solvent polarity.
£ =900)
1-Iodobutane.
Trimcthylaminc, Amax = 227 nm ( (II) K-bands (German, konjugierte)
The bands pertainin g to n transition s in molecule s containin g
3.1.3.3 SELECnON RULES conjugat ed rr system~ such as
Certain electronic transitions, which would at first sight appear
. ' butadicnc or mesityl oxide, are referred to as (K-bands. German, konjugic
to be possible , arc not generally rte). They arc characte rized
observed in the ultraviolet spectrum. Conseque ntly certain restrictio ns by high molar absorptivity (Emax > 10,000).
called "selectio n rules" arc
operative which arc as follows:
' (Ill) B (Benzenoid) and E (Ethylen ic) bands
j'f nae transitions which involve a change in the spin quantum number of an electron during the The B and E bands
ll'IDSition arc not allowed to take place or ·arc forbidden. are character istic of the spectra of aromatic or hetcroaromatic molecul es. All
bcnzcrioid compou nds exhibit E and B bands representing
00 Tbe sccoad rule is related to the multiplicity of states. According to this rule, singlet-tr n:"' transitions. For example . E 1 and
7 lrlDSitions arc forbidden. iplet • E2 bands of benzene occur near 180 and 200 respectiv ely and their molar absorpti vity varies
~tween 2000 and 14000. ---
The third rule. pertaining to forbidden transitions, arises from the symmetr {1\
y of electronic The B-band occurs jn the region from 250 to iss 11!!1,as
1t11e&. For example, the transition of a non-bonding electron to a a broad band containi ng multiple fine , 7
state in formaldehyde is stru~ture and represen ts a symmetry-forbidden transition which bas finite
bbiddai by local symmetry. but low probabil ity due to \
forbidde n transitio ns in the highly symmetr ical benzene molecule . The vibrational fine structure
'Condon nde and/orbidtkn tran.sitions appears only in the B-band and disappears frequently in the more polar
solvents. _/
Coadonl.Z~ •
liag an •~~nan t rule for understanding the nature of electronic 3.1.S The absorp tion laws and measurement of absorption intensi
g_t. pn11e1p~ el~nic ti:ansitions will take place only when ty
• candy different tn the two states and where the nuclei have
J.J.5.J Absorpt ion laws
The absorpti on of light by the molecules is governed by the followin
1
~ . ~ wbeni.the intemucleat
IIIIY'C • &Dificant velocity.
distances arc significantly different g laws:
(a) Beer's law
It ltates that the fraction of the incident light.absorbed.is proportional
to the number
of the absorbin g
lllol~ules in the iight-path and will increase with increasing concentration or
.,,.,,.
~-
1
' . . sample thicknes s.
lftj..,JJ1.MiOJaw..fJlD.-Now:Yorlc, 1929.•
•A. Burawoy. Berichtc, 63 (1930) 3155; J. Chem. Soc., (1939) 11n.
--....
"'~
,.......
126 --...
ORGAN IC SPECTROSCOPY. ULTRAV IOLET SPECTR OSCOPY 127
,.1.6 Impor tant useful terms concerning ultrav iolet spectr oscop
Jtl} Lambe
It stat"': thatrt's law
the fr.tction of the monochromatic light al,solbe d by a homogeneous medium Is '?depen
•
y
d,~
?f the mtens_ity of the incident light and each successive unit
layer absorbs an equal fractton of_llthi 3. t.6.1 CHROM OPHORE S ANO AUXOCHROMES
Fromt on
incJden these '
,t. laws, the following empirical expression, known as Beer-La mbert law, may be fonnula1c
• <1 •
(II{Chromophores
The colour ~ substa~es •
owe their colour
log10(1Jf) =Eel= A for electro nic absorpt ion.
to the presence of one or more unsaturated groups respons ible
where.
1 = intensity of the incident tight = These groups
C N, C•N, C = 0, N = N, etc; they all
arc called chromo
absorb
phores.
intensel
Typical exampl es are C = C, C-=C,
y at the short wavele ngth e~d of the
1 = intensity of the emergent light
0 spectrum .but some of them (e.g. carbonyl) have less intense
bands at higher wavele ngth owing to the
£ = molar absorptivity participation of n electrons.
=
c concentration of solute in moles/litre
l = path length (cm) (IJY'Auxocl1romes
An auxoch rome is an auxiliar y group which interact s with
A= absorbance the chromo phore causing a bathoc hromic
shift. Typical exampl es arc amino and substituted amino
groups (NH2 • NHR and NR:z), hydrox y and
LJ,nilati
-The ons mbert
Beer-La law is ngorously obeyed • provide alkoxy groups. •
d a single species gives
• • to
rise the observed In general , an auxoch rome is a group that deepens colour;
its presence causes a shift in the UV or
absorption. However, the law may not be obeyed when visible absorpt ion maximu m to a longer wavelen gth.
(i) different forms of the absorbing molecules are in equilibr The most conspic uous propert y of an auxoch romic groupin
ium g is its ability to provide additio nal
(ii) solute opportu nity for charge delocalization and thus providing
(iii) there isand solvent form association complexes
a thermal equilibrium between ground electron • • • excited states.
smaller energy increm ents for transiti on to
ic state and a lowlym g excited state
(iv) the compounds are charged by irradiation (fluorescent It will be apparen t that a charge delocalization indicate
compounds) • , , d by the contrib uting structu res is greatly
enhanced by
3.J.5.2 Measurement of absorption intensity
The intenSity of absorption is directly proport ional
aransition will have£ values greater than 10000 while those
to the transition probability. A· fully allowed
with low transition probab ility will have )C=C -C=O -
0
"-C- C=C -0
e
I I / I I
e values less than 1000.
The wavelen gth of light corresponding to maximum absorption•is designated
and can be read directly from the horizon by the symbol Amu the presence of electro n donating-NR group as
shown below:
tal axis of the spectru m as shown in the ultravio let spectrum 2
of vitamin A (An.a= 324 nm) (Fig. 3.7). The vertical axis of the
(A). which is the logarithm of the ratio JJI. The term 1 is the intensit
spectru m measures, the absorbancc .':""'\._ ,--..._ rr
R2N..1.C::::f:C3....C-O e e
0 y of the light beam which strikes +--+ RzN =C-C =C-0
1bc sample and I is the intensity of the beam after it has passed I I I I
through the sample . I I
CH20H The added opportu nity for stabiliz ation of the excited st~te brings the lowest excited state
closer to the highest ground state and thus permits
a lower energy (longer wavele ngth) for transiti on.
In general, if an auxoch rome is attached to a carbon-carbon
double bond. a bathoc hromic effect
will be observe d and if to the double bond
I =
where n electrons are available (e.g. C 0). a hypsoc hromic
'1"\..
, I effect results. Some exampl es of auxochromic
effects are given in the Table 3.1.
I
I
I
I Table 3.1
I
I
I Auxochrome Unsubstituted
I J..m., Substituted A,,,;u
chromophore (nm) chromophore
200 250 300 350 (nm)
Wavelmglb, A(am) -CH3 H 2C =CH- CH= CH2 217 H~C =CH- CH= CHCH3 224
fl&, 3.7 Measurement of A_ In the UV spectrum or vitamin
A.
-NEt2 H3C-C H2CH2CH = CHCOCH3 228 Et~NCH = CHCOCH3
-OR H3C-C H = CH-CO OH 307
1bc wavelength in the ultraviolet region is usually express • 204 H3C-C (OCH3) = CHCOOH 234
ed in nanome ters or millimicrons. -Cl H2C=C H2 175 H:!C=C HCl 185
1 nm -= lmµ = lo-' meter • 1()·7 cm = JOA
 ---- U1,11u v10LET SP1:CTRO~OPY 129
Hyperchromic
12s ORGANIC s~~"--------
J.1.6.2 8A1110(1IROMIC SJIOTAND H\,s()CIIROM1C SHIFT
sh;ft of an ,_.,.
c,r1'1ho<h-k maximum
shift io_'?"S" wavelen&lh is• called bathoch~mic _shift. II is produced8111
((ltd shift)

?-
-~
.9
HYi>"<hromi, - . i
(blue !hift) \
t.... Ba1i,xhm"'"'
(ttd 11ufl)
, ,i,.nge of .,.i;uin c,-_,., "'ns,oons underB<> ba1hochrom1c shift w11h an increase in the pol 1
of 1he ,oJ,cnl) or wh<l' ,n auxochron>< is ,nached 10 a carbon-carbon double bond. E1hyle
,..,..,,~ ,!,s(l<W" J7l ~"' in comparison IO J.boiene (A,.,• ISS nm) orisobuiene (A,., • 1s~• "

bi
1 j<
The 1,1,t,och,.,.< shift ,s progicss1ve ,s lhe number of alkyl groups increases. • nn,).
'°
a,nve,,ion of ph<l"I lhe -ndin& anion resulls in a balhochromic shift of 1h E
bind< o f - .,;111 an i_... in'-because lhe non-bonding electrons in lhe • e ' ~nd 8 100 200 300 400 SOO 600 700 800nm
for ;,rtenction ,.;1h ,1,e ,~Jectton syslem of lhe ring. anion are av11Jab1,
Fig, 3.8 Errects or substiluents on the position and intensity or an ah5orption band.
E2 band B band -
-x;-;;.; (nffiJ (by{ypochromic ef!ect .
compound i;;;; 1450
-
~tnffiJ 6200
270 It is the effect leading to d_ccrc~scd absorption intensity. For example. the intensities of pnmary and_
210 287 260()
9400 secondary bands of benzo1c acid arc decreased in bcnzoate (Table 3.2).
Phenol 235
fhenOlate anion
(;/lsosbestic point . . .
~ypsochromic shift (Blue shift) A point common to all curves produced m the spectra of a compound taken at vanous pH valuc:s 1s
Ashift of absorption maximum to shorter wavelength is known as hypsochromic shift. This may be
called isosbestic point.
caused by a change of medium (n ,rt- transitions undergo hypsochromic shift with an increase in
The anilinc-anilinium or phenol-phcnolatc conversion as a function of pH can demonstrate the
the ~larity of solvent). Acetone, for example, absorbs at 279 nm in hexane; in water Amax is 264.5
presence of the two species in equilibrium by the appearance of an isosbcstic point in the UV
nmlThis blue shift results from hydrogen bonding which lowers the energy of the n orbital. This can
spectrum. If the two substances, each of which obeys Beer's Jaw, are in equilibrium, the spectra of
also be produced when an auxochrome is attached to double bonds where n electrons arc available
all equilibrium mixtures at a constant total concentration intersect at a fixed wavelength. This point,
(e.g. C=O).) termed the isosbestic point, is the wavelength at which absorbanccs of the two species arc equal.
This is illustrated in the following table. 4-Mcthoxy-2-nitrophenol, as a function of pH, illustrates a good example for isosbestic point (Fig. 3.9).
0 0 ;O H-C;O
Compound H-C;
'H
H-C;
'NH2
H-C'OH 'ct 70
Diluted with
0.INNaOH
20S 235
A..,-i 29S 20S 60 pH 8.09
\ (Buffered)
3.1.6.3 ffYPERCHROMIC EFFECT, HYPOCHROMIC EFFECT AND ISOSBESTIC POINT
so \ \.,,, pH7.68
(,,{Hyperchromic effect g 40
It is che effect leading to increased absorption intensity. For example, the intensities of primary and
IC00lldary bands of phenol arc increased in phcnolate (Table 3.2 and Fig. 3.8).
Tablt ll Hyptrchromic and hypodttomic effects in phenol, ~nzoic acid and their salts I~ '
pH 7.02
':'\
• c.ompo.t Primary band Secondary band 20
A..,.(run) e..a A_(nm) e.,..
10
210 6200 270 1450
OOff
0 .___......__ _.__ __.__-"'-_
0~ 235 9400 287 2600 300 400 4.50 500 550
)., nm
OcooH 230 11600 273 970
oc:J 224 8700 268 560
•11:, 3.9 The spectra or 4-metho.,,·-l•nitropbenol
' .
a function or pll
 ....
Ut.TIUVIO f.eT SPECTROS COPY 131
130 ORGANIC $rt,"C11l0S coPY
tube which cover lhe required wavelength range; a tungsten-filament lamp• for
3.1 .7
The Ultravlol scanning the visible
e,,enri•I featu"'
et-vlslbl• spectrom
of ,n ,01on,a1ic eter pt,otoelectric oliuviolet •visibl•
-,ding region (350 nm lo about 800 nm) and I hydrogen or deuterium discharge tube
spectrome le, (Fi
ultraviole
ro, scanning the near
t region (about 185 nm to 390 nm).
J.IO) ,,. ,s folio•·" The discharge lube has a quartz window and contains hydrogen or deuterium
& gas under pressure
(i) Radiation source covering the required wavelength range. (when the pressure is low, line spectra are emitted while continuous spectra
...
are obrained at high
tii) Sample and reference cells. pressure). An electrical impulse of certain voltage is applied to a pair of electrode
(iii) Monochro mator for selecting a narrow s inside the ~be,
which excites the gas molecules and causes them to emit a continuou s radiation
(iv) Pho•ode«>C'"' capable of measuring theband of wavelengths.
in-ily of ,adiation beaffl 1ransmi11ed through in the UV region.
Deuterium lamp is used when high intensity is required.
• For measurements below 200 nm, the optical
(v) Amplifie< and ,cconle,-an ooipol device io ,ccord lhe measured quantity in aorrn. properties of air must be taken into considera tion.
a suitable, The oxygen molecules absorb strongly at waveleng ths shorter than 195 nm and must be excluded if
measurements are lo be made in this region. In many spectrometers, it is possible
to purge the optical
system with dry nitrogen to eliminate oxygen-absorption and thus extend the
mos• ,uitable
TheRadiation
(i) sow= of ,adi,tion .,. ,ung,ien-filament lamp and hydrogen or deuterium dischargc
source to approx;,nately 160 nm. For studying
range of the instrumen t
the absorption below 160 nm, it is necessary to evacuate the
entire system and this usually requires an instrument especially designed for vacuum
UV spectro5COPY·
(ii) Sample and reference cells
In recording the absorption spectra, identical cells made up of quartz or silica
Beam splitter \ are used {glass can be
used for visible
r 7 region). The monochro matic beam is split into two parallel
mirror system: the reference beam passes through the one containin g the pure
beams by means of a
solvent and the other
through the solution.
In actual practice, a portion of the solution, under examinat ion, is transferre
Prism Deteet«
d into a silica cell
which is then placed after the monochromator to avoid fluoresce nce or possible
decompo sition due
to absorption of other high energy wavelengt hs of unresolve d radiation . A second
M /J:5......--=-==--I!.\ silica cell containin g
only the pure solvent is also placed along with the sample cell and both are mounted in a special
holder in such a way that two equal beams of UV light are passed-on e through
the sample cell and
the other through the solvent cell.
Radiatioa
Sour0e (iii) Solvents used and co11centration of the solution
Rc:ccrder
Electroaic Choice of the solvent
amplifier The choice of the solvent depends on the following factors:
""-> I I (a) The solvent used should be of high purity, generally referred to as ..spectrogr
adc... Care should
Mot0r be taken to keep lint and dust from contamin ating the final solutions .
(b) A good solvent should be transparent over the desired range of waveleng
ths. Usll3lly solvents
which do not contain conjugated systems are most suitable for running the
ultraviole t spectrum . The
~ ,,
solvents commonl y used are water, 95% ethyl alcohol and n-hexanc . Each of them is transpare nt in
the regions of ultraviolet spectrum where interesting absorptio n peaks from
absolute molecule s are
Ugbt likely to occur.
Anode (c) Another factor pertains to the fine structure of an absorptio n band de~nds on the polarity of
the solvent. A non-polar solvent docs not form hydrogen -bond with the solute and the spectrum of the
solute clearly approxim ates to its spectrum in the gaseous state. In a polar
solvent. the hydrogen
bonding forms a solute-sol vent complex and the fine structure may disappear
-i Pbococalbode . The compoun d should
I
Multiplicalioa of electrons in
e a be a good solvent for dissolving the organic compoun d (sample).
Photocell
• pllolomultiplier IUbe
*Compact tungsten-halogen sources in a quanz envelope' arc now-a-days preferred
as they give higher emission
Fla- 3.10 Double Beam UltraYlolet Spectrometer. In the ultraviolet region than the older filament lamps. which were restricted to measurem
ents above 360 nm.
 JIii 1/
132 ~.::..:.: .------- --
ORGANIC SPF.CTROSCOPV ULTRAVl(){ET SPECTROSCOPY 133
•• ,, u.,ii(l :;:~~~~-
(d) A solvent should be chosen so that it docs not react chcmil:ally .:.:;: J.2 FACTORS AFFECTING THE POSITION OF UV BANOS
The near ultraviolet cut-off wavelengths (~t nm) for some of the common solvc:nts arc giv
below,
'\
'" J.2.1 Conjugation
,cm Cu1-01T wavclcnglh (A,.,.. 0-;;;;---
A conjugated system requires lower energy for the n n:- transition than an onconjugated system.
for example, in the conjugated butadiene (A,,.. = 217 nm; e ,.. 21000). the ,c and ,re orbitals have
Sol•
210 --- energies much closer together than those in ethylene. resulting in a fower excitation enet"gy. This may
., I
,r.10
Acctonitrilc bO explained as follows:
n-Butanol 210 A simple olefin such as ethylene has only two orbitals; one ground state nbonding orbital and one
Cycloheunc 210 excited state ,re antibonding orbital. The energy difference between them is about 176 kcaVmole.
Ethanol 210
Butadiene, however, with four ,c electrons has four available ,c orbitals. two bonding (fCi and ni)
Ethyl ether 210
210 and two antibonding en; and n; ). The n 1 bonding orbital encompasses all the four ,rclectrons ovc:t"
Heptane the four carbon atoms of the butadiene system and is somewhat more stable than a single 1C bonding
Hexane 210
)so-octane 2JO orbital in ethylene. The ni orbital is also a bonding orbital, but is of highc:t' energy than the n1 orbital.
Water 215 The two tr- orbitals en; and n;) arc respectively. more stable (n 3 ) and less stable (n;) than the
Methanol 225 ,tf orbital of ethylene.
Dioxanc 245 Energy absorption, with the appearance of an absorption band. can thus occur by a 11:i {bonding)
Chloroform
Carbon tctnehloridc
265 ni (anti bonding transition, HOMO to LUMO), the energy difference of which ( 136 kcal/mole) is
270 less than that of the simple 1t n:- transition of ethylene ( 176 kc.al/mole). giving a l _ at a longer
N.N-Dimcthylformamide 280 wavelength (217 nm). A schematic representation of electronic excitation energy levels in ethylene
Benzene 295
Xylene and butadiene is shown in Fig. 3.11.
300
Benzonitrile
0000
305
• Pyridine
0-0-00 ~:
330
Acetone 380
Niuomethanc
Con«nlration of the solution
00
C-C·-··r·-· 0G00
Normally, about O.J 10 JOO mg of the substance is required for running an ultraviolet spectrum. -r-c-c-c -c ~·
Solutions of Jer' to J0-2 molar concentration may safely be employed. However, for reliable results,
die pcrc:cntage transmittance of the solution should range between 20 and 65% in most cases. At high
00 176 kcal
13608 0G )
kcal
coacenlntions, the amount of radiation transmitted is low, increasing the possibility of error.
001
C-C··· ••
.. f}J) ..
(w) D««,or, Amplifier and Recorrkr
:Jlllotaahelric or photomultiplier wbes are generally used as detectors. Such a tube has a quartz
tr
GG GC::J0G
.000
0-0-0-00 ~,
IO admit UV radiation, a semicylindrical cathode containing an alkaline earth oxide coating
Ethylene
1• anode to collect the electrons. •
pboladeelric cells. thus. receive an intense beam from the reference cell and a less intense
.. 6am die ample cell. This results in the generation of alternating currents which flow from ~c
1...,~j cfric ceUa to an electronic amplifier. The ampliti~ is coupled to a small servometer which 1,3-butadienc
4d-. aopdcal.weda e into lbe reference beam until the photoelectric cell receives light of equal Fig. 3.11 Molecular orbital energy levels and energ_v of ,.__. transitions
-~• •ldm flam die umple u well u the reference beams. The two signals are then amplified by in ethylene and 1,3-butadieoe.
. . . of clyaocla and fmally an absorption curve relating wavelength (abscissa) and absorption
(onliule) Is ploaod on a recorder. • It is to be expecte~ that the greater the number of bonding ,r orbitals. the lower will be the energy
•
between the highest bonding norbital and the lowest excited n- orbital. The obvious e:<tension of this
in terms of Amax is that the greater the number of conjugated double bonds, the longer the wavelength
of absorption.
A,
------ L
 134
--
OROANIC SPECTROSCOPY ULTRA VIOLET SPECTR OSCOP Y. t 3S •
Conjug
Conjugation wilh a he«ro-atom moves 1he
0
--- '.t8 hi
e 3.3 Ab.forptlon of awb~nun~ (in ~thanol) .I
ation with a hetero- atom n--> tt' abs<>!J 'rion of e1 hylene • longe_r wa velen gtHs, e.
CH =CH- OCH, and CH,= ca-NM •, have.. .,., 190
and 230 nm respccuvely (E - 1000o~· --- 1tt transition
, 1t" transiti on
--
Me1hyl
2 vinyl sulphide absorbs al 228 nm (,;.., = 80()()). '"lnu
• rrans-t~omer (VI) 320 tmu
3.2,2 Effect of sterlc hindrance on coplanarlty (sttirl< cis-isomer (VII) 21300 Arnn Emu
Inhibition of reson ance) th 281 443 510
The ultraviolel speclJOScOPY is very sensitiv e to disiorri on of 5260
1he chrom ophore and conseq uently 433 1520
sieric repulsio ns which oppose !he coplanarilY of conjuga 1ed
by comparing iis UV n-elecb 'On sysiems can easily be det e 3.2 .3 Co~form~~lon and geom etry In polye ne syste ms
,pecuum wilh Iha! of a model compo und, Distort ion of the chrom ophorcCCtC<J
lead to n,d or blue shifts depending upon 1be narore of 1h< dislorti on. Th• strained molecule verbe rnay In Io ng-cham conjug
. . . ated polyenes ste • h' d
• ric ranee · ·
(I) exh1b11S a maximum al 245.5 are present. :his IS illu5trat~d
in to coplanar1ty can arise when c1s-bo nds
nm wherea s 1he usual calcula tion shows a value of 229 n nen, by the natural ly occuri ng bixin ('all trans' methyl carotenoid) and
doene (ll) m1gh1 be expecie d to have a maximu m al 273 its isom_er wit~ 8 central Cl~-~ouble ,bond; in the
nm but distortion of the chro m. The latter the long wavelength band is weakened
presumably oul of planarilY wilh ronsequen• Joss of conjuga
1ion, causes the maximum to :opho re, and a diagno stically useful cis-band probably due
to a partial chromophore. appears at shorte r
dJ
wavelength.
a ..
220 nm w11h a similar loss in iniensil)' (,;.., = 5500).
85 e as low
J.2.4 Solve nt shifts in polye nes (alkenes) and enon es
(keto nes)
The position and intensity of an absorption band is greatly affected by the polarity of the solven t used
for running the spectrum. Such solven t shifts are due to the differences in the relative capabi lities of
II the solvents to solvat e the ground and excited states
I of a molecule.
The follow ing pattern of shifts are generally observ
Another example of steric inhibition of resonan ce is afforde ed for chang es to solven ts of increa sed
d by biphenyl and its 2-meth yl and polarity:
2,2'-dimethyl analogs. Biphenyl (III) is not exactly coplan
ar (the two rings being at an angle of
approximately 45°) and in 2-meth ylbiphenyl (IV) the two (a) Conju gated dienes and aroma tic hydroc arbons
rings are pushed even furthe r out of exhibi t very little solven t shift.
coplanarity resulting in the diminished ,r-orbital overlap in
IV leading to a blue shift and diminished (b) a, /j-Uns aturate d carbonyl compounds display
two differe nt types of shifts. (i) 'rt:- Band
intensity. Addition of more methyl groups is compli cated moves to longer wavelength (red shift) while (ii) n
by the bathochromic effect of methyl tr:- Band moves to shorte r wavelength
groups themseleves. The effect of forcing the rings out (blue shift). '
of coplanarity can be observ ed from a
comparison of the absorption characteristics of biphenyl (III)
and 2,2'-dimethylbiphenyl (V) whose
. t. '"
These sdfven t effects may be due to the effect of solvati
absorption chracteristics are similar to those of o-xylene. on on the relativ e energi es of n:. n and 'rt:-
orbitals in a, /j-unsa turated carbonyl compounds. This
is described as follows:
(i) Solvat ion by a polar solvent stabilizes n, n and
tr:- orbitals.
' (ii) The stabili zatiqn of non-bonding orbital s is particu larly prono unced with hydrog en-bon ding
CH3 solvents (such as water or ethanol). The non-bonded
CH3 ' electrons on the oxyge n
.
H3C
)C=O : H-O R
will co-ord iante with hydrox ylic solvents, thus loweri
w (iii) ,,,. Orbita ls are more stabilized by solvation
ng the net energy of the n-clectrons.
r
as compa red to ff' orbita ls presum ably becau se
tlimilar interpretation may explain the behavi transit ion has a polar excited state which would natura
our of trans-a zobenz lly be stabili zed by hydro gen bondin g
ene (VI) and the sterically in more polar solven ts.
cis-isomer (VII) (Table 3.3). Such differences between cis
value.
,!_ and trans isome rs are of some
6+
. ::;c= =0~ c~o
-- • N=N ,
The net results of solvat ion (Fig. 3.12a) is that the energy of ,c ,,,. transit ion becom es less with
OHHb
solvat ion (red shift), while the energy of n
. I / tr" transition becom es higher (blue shift).
3.3 CHARACTERISTIC ABSORPTION OF ORGANIC
COM POU NDS .
.I • 3~3.1 Saturated compounds containing exclusively the o elect
VI
8•n~ the energy requir ed to bring about a rons
VII
<J 0- transition occurs in the far (vacuu m)-UV region
(
 P'- o,wANIC 5p<C11Ro0Col"'
E

~ II
I -,.,., Compounds containing carbon-carbon multiple bonds
ULTIU Vl()LET SPl:CTROSCOPY 137
~T' i I"'T ,r; ,r-+ > ....... ,r; J.J.3.1 ABSORPTION OF NON-CONnJO/\TEO AND CO'."fJUGAITED ALl(ES'E..!J
L ·II j i .. -~ .. .;
(a) Absorption by non-conjugatt!d alA:t!nt!s
All non-conjugated alkenes have an intense absorption due to ,r-,. 1f.4 transition below 200 nm. For
example. ethylene absorbs in the vapour phase at J65 nm (t;_.. = 10000). A 5ee0nd band near 200 nm
may be due to the elevation of the two tr electrons to tr- orbitals.
•j_ I JI, Alkyl substitution of parent alkene moves the absorption to longer wavelength5. This balhochromic
LcsS polar ,olWIII Mc,re polar ,ol¥eal effect of alkyl substitution is due to the extension of the chromophorc.. in the sense that there is a
die re)adff enerpes of ,r, 11 and It'- orbitals ln small interaction, due to hypcrconjugation. between the u electrons of the allcyt group and the
fll. 3.12a Effed ot ..,,.,..doa OD chromophoric group. This effect is progressive as the number of alkyl groups ruc,eases.
c:r, p.a,,sararated ketoaes- The intensity of alkenc absorption is essentially independent of solvent because of the non-polar
. thesC cransitions remain transpar~nt in the near-UV region. Mc~ nature of the alkene bond.
in the range from 1»-~nm. le. display a-, tranSition and Amax for each of these comnnu...
propane. eycloheUJIC ere.. ,or exarnp ,.. -...q 1
(b) Absorption by conjugated a/kenes
is below 140 om.
(I) Types of conjugated alkenes
J.3.2 Saturated compounds containing hetero-atoms _
=
The various types of conjugated dicnes arc described briefly as follows:
saturated compounds containing hetcroato~ such as oxygen. mtrogen. sulphur or the halogCl!s,
non-bonding electrons (nor p electrons) and can give rise 0- transition of an clectr1:11 (i) Acyclic diene or heteroannular diene
Jone pairs of hcf,eroalOm. The absorption maxima of most saturated oxygen and chloriit Most acyclic dienes have transoid conformation (I). i.e. trans disposition of double bonds about a
compounds occur below 200 nm. Alcohols, ethers and alkyl chloride (CH3CI) absorb at wavclcngn single bond. The base absorption is 217 nm.
shorter dwJ 185 nm and arc. thcrcfore commonly used as solvents for work in the near UV rcgiCl
Sulphides. disulphides. thiols, amines. bromides and iodides may show weak absorption in the IICf C
UV. Frequently. the absorption appears only as a shoulder or an inflection. In compounds containin, c-c~ ,Qc-c~
two hdaoalomS having overlapping lone pair orbitals, the absorption_ is shifted to longer wavelcn~ c~ ~c
C
la contrast to the divalent sulphur compounds, hexavalent sulphur compounds, e.g. sulphoncs. transoid (s-traos) c:isoid (s<is)
.sulpboaic acids and esters and sulphonamides are essentially transparent in the ultraviolet region a I IV
die remaiada of the molecule is saturated.
Ablorption data for several saturated compounds containing hctcro-atoms· are given in the Tablt A heteroannular diene, however, is a conjugated system in which the two double bonds arc
1.3A. confined to two different rings (m. However. these double bonds arc exocyclic. one of them being
exo-to ring A and the other exo-to ring B. The base absorption of II is 214 run. Hctcroannular and
Absorptlo,u dw to /wterr,-atotns in sa1ura1ed molecules (n ~)
acyclic dienes usually display molar absorptivities in the range 5000-:?0000.
Stample A_(nm) E.-
Nedwd
Mclbylamiae
177
215 :,.
200
G0 ll
0 Ill
1-:'fe'enedliol 224(s)
Diedayllulpbide 210 1800
-1~ (ii) Homoannular diene
-230 In the homoannular diene, the two conjugated double bonds are confined to a single ring (lll}. i.e. the
202 21~1
·• ,20 cyclic dicnes arc forced into an s-cis (cisoid) conformation (IV).
252
301 ' This type of diene has a base absorption at 253 nm and displays molar absorptivities in the range
295
Ji:.-ipbide
334
181 of 5000-8000. Homoannular dienes contained in other ring sizes possess difterent base absorption
. cbloride pbide 'tfJ values, for example, cyclopcntadiene (228 nm) and cydoheptadiene (2-U nm).
173
~~lnmide 301
iodide 208
259
 ULTRAVJ0LET SPECTROSCOPY 139
-;:be, 3
and co-workers re!""ted that lhe ultraviolet ab,orption spectra of 1he dienes which exhibit
otecular ?vercr~wd,ng or ring strain behave anomalously. For example, the calculat~ .A.mu va~ues
138 ORGANIC SffCTR()SCOl'Y
1
In die ,.,.;cycle dicnc. one of 1ht double t,oncls forms part of a ring and !he other is exocycl' . show deviations
and VIII from Woodward's rules due to stenc interactions
(iii) StmiC)iclt ditnt for the strained d1enes• VII
,n
1•
.
n
°""idc lhe ring sh<>"". in ,uuctut< V. When ~ly__on_~.9f_lhe _tw~ sp~hl'.J!!idizod Carbons • or as well as some spec,a interactions occuring in the cis conformatio
- n118Jl~n51dcrauon, !uch a double bond • --is called an cycu, of,
a
. cloublc bond is a15part of the ·--:--exo
0 • VII
D vm
~•220nm -\-•248am
V ·- ti-•5500 ,_.15,00
3.3.3.3 ALKYNES, POLY-YNES AND POLYENYNES
cross-conjugattd systtm
In cross-conjugated system. as represented by the partial structure VI, the more reliable prediction
I
arises from the ~hromophore that is ~ore highly substituted, i.e. giving rise to the longest wavelen·gth (a) Alkynes
absorption maximum. , • The ultraviolet spectra of alkynes are, in general, more complex than the corresponding alkenes.
Acetylene shows a relatively weak band at 173 nm; the position of l__ of alkylated derivatives is
shifted slightly to longer wavelengths.
=C VI
The conjugation of acetylenic bonds results in very characteristic spectra consisting of two principal
bands in the near UV region; the short wavelength band is extremely intense. They arise from
transitions and are associated with fine structure. When more than two triple bonds are conjugated,
the spectrum exhibits a series of very intense bands separated by regular intervals and a series of
(II) Absorption by conjugated alkenes
When two or more C= C units arc conjugated, the energy difference AE between the highest bonding medium intensity bands at longer wavelengths. As the number of triple bonds in conjugation increases,
,rorbital and the lowest excited 1t" orbital becomes small (Fig. 3.11. page 133) and results in a shift the wavelength of the highest intensity band shifts bathochromically (Table 3.5).
of lax to longer wavelength (bathochromic shift)..
This concept helps to distinguish between the two isomeric dienes, 1,5-hexadiene and 2, 4- Table 3.5 A.-.r Valuts for poly-yMs CHJC=C),.CHJ in tthanol soluzion
hexadienc, from the relative positions of Amax.
n Amax (more intense band) run
Hz( =CH-CHz-CHz-CH=CH2 CH,CH=CH-CH=CH-CH3
l.S-Hexadicnc 2,4-Hexadiene 207 135000
3
(conjugated diene) 234 281000
(non-conjugated diene) 4
s 352000
A.a= 178nm . Amu=227nm 260
445000
6 284
As 1be aumber of double bonds in conjugation increases, AE for the excitation of an electron
to become smaller and consequently there will be a continuous increase in the value of • (b) Polyenynes
tiheCODjupled double bonds, as in vitamin A, the absorption is moved into the visible part Acetylenic compounds, in which triple and double bonds are in conjugation, exhibit absorption
Dyes owe their colour to the presence of conjugated systems which have strong maxima similar in shape to those of poly-ynes. The intensity of the long wavelength group of bands,
1¥ilibleqion.
is, however, greater in the case of polyenynes and both groups of bands display a bathochromic shift
relative to those present in the spectra of poly-ynes of the same chain length. Conjugation of acetylenic
Dll!ltP.S IN CYWC SYS'reMS
~nd ethylenic bands in vinyl-acetylene, for example, gives a band at 219 nm (E = 6400) having a
• a ring lyatcm absorbs at much higher wavelengths than predicted by the shoulder on the long wavelength side. Further conjugation with ethylenic bonds shows absorption
C)'cloheu-1.3-diene. for example, exhibits a maximum at 257 nm and the similar to that of the polyenes.
i'--.8000
1
) ii CCJlllidenbly lower than that of the acyclic diene. Aprobable reason for this
! i!DII.,._ • tbe ciloid conformation (cis disposition of double bonds around
mCOllbllt lO tbe lllnloid conformationofmost acyclic dienea. However, the wavelength
~ - w i d a iaaaain, rin, size. For example, cis-cis-cyclodeca-1,3-dienc does not
~210 am. l'Oblbiy the cbromophorc ia forced out of coplanarity by the ring
1
3• W.P. Forbes, R. Shihon and A. Balasubramanian. J. Org. Chem., 29 (1964) 3527.
ii
~....;
140 ORGANIC SPECTROSCOPY
---........
3.3.3.4 WOODWARD-FIESER RULES FOR CALClll.ATINO Al\SORl'1'10N MAXIMA OF UNSA1'\l~l\l'~I)
HYDROCARBONS
---
ca/culntloll of Am,u (11m)
ULTRAVJOLET SPP.CTROSCOPY 141
Bnsic AmAJI value
Calculation of absorption maxima for u11sat11mted conapollnds M • number of substituenr1 • 114 nm
The absorption maxima for a conjugated or substituted diene can be predicted by using the dnta give n • number of conjugated double bonds • 10
in the Table 3.6. • n Rendo • number of rings with endocyclic double bonds - 211
:a
Reiio • number of rings with exocyclic double bonds :a 0
Table 3.6 \\bodwan:i and Fitser ruin fer rolculating 11/traviolet absorption ma.tima of s11bstitmed ditnts .
... A.mu a 114 +SM+ n(48.0 - 1.7n) - 16.S Rffldtr JO Rn(t
( ~,hanol solution) • 114 + S X 10 + 11 [48.0- (1.7 X ll)J - 16.S X 2 - 10 X 0
217 nrn
= 114 +so+ 322.3 - 33 - 0
(i) Parent acyclic dienc Cale. Amaii = 453.30 nm
214 nrn
(ii) Parent hctcroannular dienc Obs. A.mu = 452 nm
(iii) Parent homoannular dienc
253 nrn
Increments for substitucnts
(iv) All..")'l group or ring residue (If the all..-yl group is attached to +5 hrn Calculation of Emu
two double bonds, count it twice)
Emax = (1.74 X lo")n
(v) Exocyclic double bond (effect is two-fold if bond is exocyclic to two rings) I.+ 5 ' nrn = 1.74 X 11 X 104
(vi) Double bond extending conjugation
' l , ·• + 30 nrn Cale. Emax = 19.4 x 1o"
Substituents on vinyl carbons (for each one) Obs. Emax = 15.2 X 104
(vii) Halogen (-Cl. -Br) +5 nrn
(viii) 0-(all")'l) (-OR) +6• The equation for calculating Emax is semi-empirical, the value calculated does not correspond well
0-(acyl) (--O-COR) +0 nrn with the observed value.
(ix) S-(all-yl) (S-R) + 30 nrn Some important examples which serve to illustrate the application of these rules to a variety of
(x.) N-(all.-yl)2(-NRR-) + 60 nrn conjugated diene systems are depicted as follows: •
k
Calculation of A.oz (nm) and E,,,,ufor systems containing more than four conjugated double bonds Parent acyclic diene = 217 nm
The rules depicted in the table 3.6 hold good for unsaturated compounds containing upto four double bonds. Substitucnts 2 x S = IOnm
However. for conjugated systems containing more than four.double bonds, Fieser4 and Kuhn5 suggested
the following equation for calculating the basic Amax and Emax values of UV absorptions in such systems. Cale.Amax = 21:1 nm
(nm) value can be calculated by using the following equation:
Obs.Ainu = 226 nm
Amax= 114 +SM+ n (48.0- 1.7n) - 16.5 Rendo - 10 Rexo Parent acyclic diene = 217 nm
wla'c n = number of conjugated double bonds.
Substituents or ring residues 2 x 5 = 10nm
M = number of alkyl substituents/ring residues on the conjugated system.
Exocyclic double bond 1 x S = 5nm
R.. = number of rings with endocyclic double bonds in the conjugated system. • Cale. Ainu = 232 nm
R...• llllfflhc-s of rings with exocyclic double bonds. Obs.Anwt = 237 nm
• pnil,rty be calculated with the help of the following equation: • . •
Em.a= (1.74 X lo')n .
1
Parent acyclic dicne ' = 217 nm
Ring residues 4 x S = 20nm
for example, for /karotenc (I) can~ calculated~ described below: Exocyclic double bonds 2 x S = 10 nm
;:.-.,,, ·.,. ,·; . ... : H3C
';'DJ . Cale. -l.uu = 247 nm
Obs.Amax = 247 nm
Base value (heteroannular diene) = 214 nm
CH3 Substituents or ring residues 3 x 5 = 15 nm
/karofene(f)
E:<ocyclic double bond l x S = 5nm
•.t 930 (1950). I
. . I f =l,
Cale. 1\.11." = 234 nm
r. deuuchen Chem. Oea. 71, 442 (1938).
ti
r 142 ORGANIC SPECTROSCOPY
Parent hctcroannular dicne • 214 n111 .,,-- d ULTRAVIOLET SP2CTROSCOPY 143
Double bond extending J.J.4 Absorption u, to carbonyl compounds
conjugation l x 30 • 30 n111
Ring residues 4 x 5
Exocyclic double bond 2 x 5
•
•
20 n111
IO n111 3.3.4•1 ALDEHYDE!S AND KP.TONES
, J.1 Isolated aldehydes and lcetone1
Cale.~. •
J,J,, ' lated carbonyl chromophore exhibits a 11rong •b,orption owing to ,r ,.. transition at about
Parent heteroannular diene • 214 nm /.ff''°,. and a weak 1bsorp1ion (t < 100) in the region 27S-29, nm due ,ro transition, the
Ring residues 3 x S • 15 nm J?O: des absorbing at slightly longer wavelengll,s than 11,e cormponding ketones. This weak band
Exocyclic double bond l x S • 5 nm aide yd) results from the forbidden transition of a loooely held • elcctroo to ,.. orbital, the lowest
(R-banpied orbital of the
unoccu carbonyl group.
Cale. )....1 • 234 n111
Obs. ).... • 234 n111
1 JJ.,./.2 a, /J-Un~at~rated aldehyde,, lcetone1 and their derivative,
Parent heteroannular diene = 214 n111 An isolated ethrlemc linkage exhibits a ~igh intensity (t ... 10000) ,r band (K-band) near 170
~H11 nrn and that an isolated carbonyl group displays a low intensity (e ... 20) symmetry forbidden n ft'-
= 20n111 band (R-band) near 290 nm.
Ring residues 4_ x S
--
However, when a carbonyl group is conjugated with an ethylenic linkage as in an a.~unsaturated
Exocyclic double bond 2 x 5 = 10 nm carbonyl compound, both the bands undergo bathochromic shifts to the regions 21(}-230 nm and
310-330 nm, respectively (Fig. 3.13)
Cale.).... = 244 n111
Solvent effects
The position of n 1t'- and n ,,rt, transitions in carbonyl compounds vary with the nature of the
Parent homoannular diene = 253 run solvent used. As the polarity of the solvent increases, the ,r ,,rt, bands undergo a bathocbromic (red)
shift. whereas. the n 1t'- bands undergo a gradual hypsochromic (blue) shift. These shifts arc due
-
Ring residues 4 x 5 = 20nm • to the solvent stabilization of the excited or ground electronic states, thus resulting in a change in the
energy ~ap between the levels involved in the transition. This is illustrated Flg. 3.12b.
Calc.-'-mu = 2Tirun
" • .ti Beccmcs dedroa
l
I
Parent homoannular diene =llirun ir-/c-o: deficient
Ring residues 3 x 5 = 15run
Exocyclic double bond 1 x 5 = 5run
Cale.Amax
Parent homoannular diene

= 273 nm
= 253 nm
I n °" Large solvent stabilizatiai.
} due to hydrogen bonding
double bond extending n "/
c-o:-H,
.. ..
H/Q.
conjugation 1 x 30 = 30nm
Ring residues 5 x S = 25 nm ,r • ··- - -~ - ,r
-
Exocyelie double bonds 3 x S = 15 nm
Non-polar Polar
= 323 nm solvent Solvent
Cale.A.a
Fig. 3.12b The effect or a polar solvent on an 11 ,tt tramition.
Parent bomoannular diene • = 253 nm
Double bonds extending The n ,rt, band shifts to longer wavelength or lower energy in a more polar solvent because the
coajugllion 2 >t 30 60nm
--
= 1t'- transition have a polar excited state which would naturally be stabilized by hydrogen bonding
x
Ring residues 5 5 • = 25 nm
~n more polar solvents. This lowers the energy gap between tr and ft'- levels and consequently
Blocyelie double bonds 3 x 5 = 15 nni
increases the wavelength of ,c ,,rt, band. The blue shift in the case of n band, on the other
Cale.A... = 353 nm hand, results from hydrogen bonding which lowers the energy of n-orbital.
 - ~
.!,144~~0~ R~G~A~N ~lc~S~PE~ CTR~OS~ CO~P~Y--
I 1 -- •
------------ --------
•• ,:
--- - UtTRAVIOLf T SPECTROSCO PY
causes a bathochromi c shift (when axial) or a hypsochromic shift (when cquator~af) in the;.,_. val~e
of the parent ketone (Table 3.7). The bathochromic shift is usually accompanied by a strong hyperchrom, c

145
.,•···
...•' effect.
Table 3,7 Absorption maxima for some substituted cyclohexanon u
....
It' - •
.•
- .;
. .....••J••••~ I I("
compound ,l,,,0 (nm)
ax
320nm X cq
.-J.-f+- 1t---·f ••••• y
C:t
165nm 218nm 170nm -7 + 22
0 a-Chlorocyclohexanone Cl
.•·'
!L#-1 a-Bromocyclohexanone Br -S 28
...._ _ _J_
If .-
'- + 17
a-Hydroxycyclohexanone OH
.,.._
.••--- If -12
., ...•···
2-Chloro-4-t-butylcyclohexanone affords an illustrative example. Equatorially substituted 2-chloro-
,,,. I 'c-c""
,,,,.c=c, # 'c=o=
/ _4-t-butylcyclohexanone has its n n-- maximum at a slightly shorter wavelength than that of the
-, 0C parent ketone, whereas the axial chloro isomer has a more intense absorption band at considerabl y
longer wavelength. The strong bathochromic and hypsochromic effect of an a-halosubsti tuent also is
Fl&· 3.13 The absorpdom of a simple enone ~em and those of the non-interacting chromopho~ . observed in steroidal ketones, but a satisfactory explanation for the phenomenon has. not yet been
enco\lntered.
I
5.0 (ii) Effect of auxochromic substitution
Substitution of the carbonyl group by an auxochrome with a lone pair of electrons such as -Cl, -NH2,
,..s 000 -OR or -OH, as in acid chlorides, amides, esters or acids, produces a pronounced hypsochrom ic
effect on n";•transition. This is due to the inductive effect of heteroatoms (oxygen, nitrogen
or halogen) which withdraw electrons from the carbonyl carbon, causing the lone pair of electrons on
,.o the oxygen to be held more tightly and therefore greater energy is needed for the ·n tr- transition.
Hence the n n-- band in these compounds is shifted to shorter wavelengths (200-220 nm) range.
3..5 This is illustrated in Table 3.8.
Table 3.8 The hypsochromic shifts caused by auxochromes on the n n• transition of a carbonyl group
3.0
Compound (solvent) (nm) (e,,.,J
2..5 293 (12)
CH3--CH=O (hexane)
CH3--CO-CH3 (hexane) 279 (15)
2.0 235 (53)
CH3--CO-Cl (hexane)
CH3--C~NH2 (water) 214 (-)
CH3--CO--OC2H5 (water) 204 (60)
200 220 2AO 260 280 300 320 340 360 380 400 204 (41)
CH3--CO--OH (ethanol)
Wavelaiglh (ma)
.... 114 lJlln,luM -,ectram of anthracene (A) and pbeaanthrene (B) ln cydohexane solvent. Derivatives of carbonyl compounds (oximes, semicarbaw nes a,1d
nreao1 ....,.,,,_.. 2,4-dinitrophe11yl hydraw11es)
The ultraviolet spectra of the derivatives of unsaturated carbonyl compounds exhibit absorption
- - '"' ,,,_ C4lbon •-to •~ carl,ony/ f,oup ' bands at considerably tonger wavelengths than the derivatives of simple saturated carbonyl derivatives
111 I/fled"'-
and thus give confirmatory evidence for the presence of an isolated or conjugated carbonyl group in
'lbeinll'Oduction ohn a-halogen atom (polar substituent) in an aliphatic ketone has practically n0 the molecule.
effect on r transition. However, the presence of an a-halogen (Cl or Br) in alicyclic ketones
,.. •~,
r ---...:.:=.:.:..:.:.::..::.:_::::.:.::.::.:=.._:__
146 ORGANIC SPECTROSCOPY _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _
___
Oximes absorb at approximately the same wavelength •~ the original ca~~nyl c?mpounds and
consequently are not very useful for analytical work. Sem1carhazones exh1b1t maxima Which ar tJ.Diketones arc acidic (bein1r th . ,,ln.,.... _ - - Utn,wlOl.n SPEcnt05COPY 147
,--···& me y'"Y•vgucs of c . .
,._ v1 . .
shifted to longer wavelengths by 30-40 nm. with an average increase of 10000 in the val~e of~ •
bsorption maximum undergoes I bathochrom· h.;r Yhc ICtds) and in the alkaline medium the
compared with the original carbonyl compound. ~ey are proba~l_y best for the an_alyt1cal Work
because there is least interference in th~ 300 nm reg1?n ~nd the pos1t1on of !he abs~rpt1on maxirnulll
L, • 282 nm (E • 28700). ••' 1 1• For •umpte. the anmn (V) of d;medone hu
is nearly constant and docs not vary with alkyl subst1tut1on. Also the band 1s very intense and srnau J,J.4.1.4 ENEDIONES AND QUINONEs
quantities of material may be examined. 2.4-Dinitrophenylhydrazoncs of saturated ketones absorb
near 360-365 nm whereas similar derivatives of a. /J-unsaturated ketones absorb in the region fro I) Enedlones
375 to 385 nm. They arc equally good although the position of the absorption maximum Vari Ill
slightly with alkyl substitution. Cs
~ne,liones exhibit absorpti~••. simi_lar to that of the i><l'Cnt a, ,,.• .,...,...., ketone, the additional
bony! group cxtendmg COIIJ•8•0on having no effect on the •bsorprion maximum. For example.
3.3.4.1.3 VJCINAL DIKETONES AND '3-DJKETONES ::..J-cnc-2,
(£= 9750).
5-dionc (I) absorbs at 226 nm(< • 14500) wi,,,.... pent-3-cne-2-on, absorns • 224 nm
(i) Vicinal or a-diketones CH3COCH =CHCOCH
3
In vicinal diketoncs. there arc two lone-pair molecular orbitals and two n-- orbitals and consequent! I CH3COCff ,..CHCH3
there will be two n ti- transitions in these compounds. one occurring in the usual range, i.e. 2~ Amax Hexane = 226 nm II
nm (E = 30) and the second which stretches into the visible region, absorbs weakly (E = 10 _ 30) in (Emu = 14500). ~=-224nm
the range from 340 to 440 nm. (e,_. = 9750)
In cyclic a-diketones, the enol-form is generally more stable than the keto-form and frequent! (Ii) Quinones
sho'? evidence for the existence of ~e e~l-~orm. For examp!e• cyclohe~ane-1,2-dione shows absorptio~ Quinones, though may be regarded as containing an a. P..unsaturatcd ketone system (vtnylogous a-
maximum at 266 nm (E= 2600) which 1s shifted to 294 nm m the alkahne medium. Additional doubt diketon~). exhibit distinctly different t}'pes of absorption spectra. A few representative quinones are
bond serves to increase the wavelength of the maximum, the results being predictable by Woodward~ illustrated below:
Fieser rules.
(II) JJ-Dlketones
/J-Diketones are known to exist as tautomcric mixtures and invariably show n
cbaracteristicofthoenol-form~ the keto-form showing only the weak n
in the vapour phase or in solution of non-polar solvents is nearly 90%.

,
ti- absorption
Acetylacctonc
is a classical example. The amount of the enol-fonn present in aqueous solution is about 15% and that
¢ 0()
0

0
0

0
0
p-Bcnzoquinonc Naphtbaquioooe
--
A_.Et0H244nm Allllnquiaaac
0 0 6H~ (£ = 24000)
279nm '
A_.Hcxanc
241 nm(t•20000)
..l._ElOH
243 DIil (£ • 33000)
AA
sr-- 246 DID (t: 23500) 252 nm(£-. SlOOO)
(t=400) 2S 1 DID ( Ea 19000)
-
430nm 263 nm(£• 20000)
256 DID (t: 13000) 272 nm(£• 20000)
Keto-form Enol-form (t= 20) 330 nm (t = 2750) 325 DIil ( £ ,. 5600)
1H2o 274nm Emax=2050 40S nm (£a 90)
A.::C-- 272nm Em.a= 12000 Thus, p-benzoquinone gives rise to three absorption bands in the ultravtolet visible region 3t 24-l
II nm (n ,,_. transition), 279 nm and 430 (n n- transition) in ethanol solution6 • The colour of the
I simpler member is due to the weak n re- transition.
The unusually high value of A.ma is probably a consequence of the chelation in the enol fonn (~· o-Quinones generally absorb at longer wavelengths than the cortesponding paraquinoocs7 ·1 and
The enol-fonn (IV) of dimedone (Ill), being transoid and incapable of chelation, exhibits in the acid display three absorption bands in the ultraviolet and visible region near 260 run. 400 nm and 560 nm.
medium, the absorption maximum at 255 nm (£ = 17000) which is in good agreement with the value .. The two longer wavelength bands arc particularly useful in the characterization of o-quinoocs..
predicted from the Woodwud-Fieser rule. The position of three bands arc not much effected by the polarity of the solvents and there is no
o?:i
consistent trend of the wavelength of absorption with substitution.
e
OH
•O O H ..-- E.A. Braude, J. Chem. Soc., (1945) 490.
0 0 • S. NagaJcura and A. Kuboyama. J. Amer. Chem. Soc., 76 (1954) 1003.
0
. e0o
ff.
8• H. Hartmann and E. Lorentz, z, Naturforsch, 7a (1952) 360.
Ill IV
L.
V
 -----~:::::::~~:;----------~!!::!.~~~~~~~~~~..!2
I, Cyclohexene-1-carboxyl lc acid ULTRAVIOUIT SPECTROSCoPY 149
______
148 ORGANIC:...-:...--------- -
,.,.cro••·· ,MtoES ANO LAcTAMS
SpECfROSC()PY
3.3.4.2 c.«eoX\1.tC ,c10s, ..,..,..,. ~!) Parent ct, /3--dialkylsubstituted acid = 217 nm
Ca,boxylic adds a~d their est..-S
3.3.4.2-1 Ca'11oX'•Ucac;ds ,sr,rs a weak intensity • --> ,r' abso,puon
andexhibit • band near 200 nm. Th,
11 acooH {u) • Double bond in a six-membered ring
Cale. Ainu
- +0nm
= 217 nm
band is often dis=nible onlY as a shoulder on•'"""' intense band at shorter wavelengths and i Obs. A.mu 217 nm
linle v,lue for diagnostic pwpOS<'· ttoweY<r, in thioether>, the carbonyl group and the sulphur43a: of
:s
inte,,ct_ to give a t,,nd at 50,newh" higher wavelength (e.g. butyl d"oacetate has ,1,.,, 231, E ~m z. Cycloheptene-1-carboxylic acid
Coniusarion of a c,rt,oxyl or alkoxycarboflYI (ester) group wtlh • double bond results in ah" ),
intensity n-+ 1f' abSOrption - 200-230 nm- For example. acrylic acid, !he first member f tgh (i) Parent system with a. p..disubstitution = 217 nm
series, displai• an intense ,1,sorption t,,nd at 200 nm (£ = ICJOOO). Alkyl substitution in thi ob th, {ii) Double bond in a seven membered ring = + S nm
stntelw< or the Pl""""' of electr<>negative group on lhe a-carbon causes a bathochro -• •sic 0-COOH
si~ilor to "- /J-uns,tuntcd ketoncs- The extension of coajugation produces further bath m~ •hift Cale. Amax = 222 nm
sh•fu """'mpanicd by ,n ;nc,case in the band intensity and lhe appearance of the fine stnt oc romic OBs. A.max = 222 nm
,t,,o,prion chu.aoristics of se-• "- JJ-unsatur,ted acids. indicating the bathochro • h_cturc. Th, J.J.4.2.2 Lact~nes
by the•-="'"" addition of double bonds, arc mustratcd in Table 3_9 _ • mtc s tfts cauSC<) The spectra of simple unsaturated lactones exhibit end absorption in the region from 200 to 240 nm.
Extended conjugation produces a bathochromic shift of the n ,,,,.. transition (K-band).
Table 3.9 Absorption characteristics 'of a, f>unsaturated acids
EtOH (nm) J.J.4.2.3 Amides and lactams •
a, ,B,:Unsaturated amides and lactams display absorption in the near ultraviolet region around 200 nm
Compound Amax Emu
(Ema~ - 8000). a, ~Unsaturated lactams exhibit an additional band near 250 nm (Ema - 1000).
200 10000
205 1400()
CHr=Cff~H
13000 3.3~4.3 WOODWARD-FIESER RULES FOR CALCULATING ABSORPTION MAXIMA OF CARBONYL
CH,-CH:CH-COOH (tranS) 205.5
CH,-CH:CH-COOH (cis) 254 25000 COMPOUNDS:
Cl 1,--(CH:CH)rCOOH 294 37000
C 1,--(CH:CH)J-COOH 332 49000 J.J.4.3. J Rules for the prediction of n -+ n• absorptions in a, {>unsaturated
CH,--(CH:CH)r(:OOH , carbonyl compounds:
The position of n absorption of a, /3-unsaturated carbonyl compounds can be predicted by a set
Calaalatioa of absorption maxima for unsaturated carboxyllc acids and esters
A set of empirical rules, developed by Nielwn9 for calculating the absorption maxima for unsaturated of empirical rules first formulated by Woodward 10 and modified by Fiescr11 and Scott. 12 The modified
rules for c~lculating the expected position of absorption maxima are depicted in the Table 3.11.
carboxylic acids and esters has been described in Table 3.10. •
Table 3.11 Rules for the prediction ofwavelength pertaining to transizions in unsazurated carbonyl compounds
Table 3.11 Empirical n,les for calculating the absorption mpima of unsaturated
6
carboxylic acids and esters
'-c=C-C=C-C=O
AmaxEtOH(nm) 6/ I I I I
S.No. C4mpound Y fJ a
(i) aar /J-Moaoalkyl IUbstituted 208 Base value for the parent system A,nu(nm)
(ii) a. /Jar /J. /J-Dialkyl substituted 217
(iii) a. /J. /J-Trialtyl substituted . 225 (I) Parent acyclic or six and higher membered ring ketone 215
·(iv) Eaoc:yc:lic: a. /J-double bond +S (ii) Parent five-membered ring 202
(¥) EDdocyc:llc a. /J-double bond ia five or seven membered ring +S (iii) Parent a \ P.unsaturated aldehyde 207
(iv) Parent a, /3-unsaturated carboxylic acids and esters 195
'A compari,on of the observecl' and calculated values illustrates the utility of Nielson's rules. (Contd.)
cycl~l-cuboxylic acid and cyclohcptenc-1-carboxylic acid as examples:
10. R.B. Woodward, J. Amer. Chem. Soc., 63 (1941) 1123; 64 (1942) 72, i6.
ll. L.F. Fieser and M. Fieser, Natural products related to Phenanthrene, Reinhold. New York, 1949.
~• A.T. J. 0IJ. Clem.. 22. 1539 (1957). l2. A.I. Scott, Interpretation of the UY spectra of Natural products. Pergamon. New York. 1964.
'.
(<
r 150 ORGANIC SPECTROSCOPY _,,,. ULTRAVIO~ SPECTROSCOPY 151
Table 3.11 Contd.
Base value for the parent system
(a) lncrtmtnt for
(i) a double bond extending ronjugation

A....~<n111i
+Jo
+ 39

ex: Parent ketone

a-Bromo subttituent
Rini residue P(one)

• 215 nm
• 25 nm
• 12 nm
Cale. Aina• '252 nm
(ii) homodienic component +5 Parent• ketone • 215 nm
(iii) cxocyclic double bond a + 10
(iv) each alkyl group or ring residue p J
+ 12 ·o a-substituent • 10nm
yand hightr + 18
JJ,substituent (2 x 12) • 24nm
(b) Jncrtmtnl for tach auxochromt a • + 35 Exocyclic double bonds (2 x 5) • 10nm
(i) Hydroxy group p +Jo
6 +so' Cale. ,l,.. • 259 nm
+6
(ii) Acetoxyl group a. fJ, or Y a i
+35 Parent ketone = 215 run
(iii) Alkoxy group p , I
+ 30 a-substituent (OH) r--= 35nm
r + 17 Ring residue ~2 x 12) = 24nm
6 + 3)
p + 85 Cale. A_. :s 274 nm
(iv) Thioalkyl p + 95
(v) Dialkylamino a ,, + IS Parent ketone =
215 nm
(vi) Chlorine p + 12 Double bond extending conjugalion =30nm
a + 25 One tJ,,substituent =12 nm
(vii) Bromine p ' 1'
+ 30 One cS-substituent = 18nm
= 5nm •
Exocyclic double bond
(c) Solwnz correaion (rtlaJiw to ethanol)
-8 Cale. ,l,.. = 280 nm
(i) Water
(ii) Methanol
0
Chlorofonn +I Parent ketone = 215 nm
(iii)
(iv) Dio.une +5 Double bond extending conjugation = 30 run
(v) Ether +7 Homoannular diene component = 39nm
(vi) Hexane + II One a-substituent = 10 run
One cS-substituent = 18 run
0 Exocyclic double bond = 5 run
J.J.4.J.2 Calculation of~ values in a variety of~ /J-unsaJurated carbonyl compounds
Some important cumples, which serve to iJJustrate the application of these rules to a variety of a, P. Cale.~= 317 nm
- • carbonyl compounds, are presented as follows:
The compound I illustrates a cross-conjugated system in which the more reliable prediction arises
.,,,,0 Parent ketone • 215 nm
c-'-C .. from the more highly substituted chromophore; i.e. the chromopbore giving rise to the longest
wavelength maxima.
-
~3 Two JJ,substituents 2 x 12 1
= 24 run
Parent 11'-' enooe = 215
Cale. = 239 nm Two tJ,,substituent = 24
One exocyclic double bond = 5
Parent a, JJ.IIDSllUrated ketone = 215 run Cale. = 244 nm
One a-substituent • 10nm Parent 111.lenone = 215
One JJ.substituent = 12
-
One JJ.IUbstituent • 12 nm Amax= 227nm
CaJc.,t...• 237nm
.. (
 ----- ULTRA VIOLET SPECTROSCOPY 153
ORc;ANIC SPECTROSCOPY - 13 1 --
_.-- Hence the predicted A.max 1:i 244 hill Braude • '·" used the symbols E and B t0 •
In fable 3.12, designate the absorption bands of benzene as depicted
R Parent ketone = 2is nm
Double bond exte.nding conjugation ' = 30 n111
Homoannular dicne component = 39 nit\ Tahle 3.12 Ab,orptlon band, of btnun~
--
One a-substitucnt = 10 n111
Sr. No A.mu(nm)
One ~substituent = l2. nm Dc5ignated H References
One S-substituent = 18 n111 184 1
Exocyclic double bond = 5 nm
1 8 or E1(second primary) 13 & 14
2 204
'La or Bi or K (primary) 13 & 14
Ac0 Cale.Amax=~ 3 256 1
Lb or 8 (secondary) 13, 14 & 15
po Parent ketone
One a-substituent
Two ~substituent

= 202 nit\
= 10 nm
= 24nm·
. -=---
Cale. Amax = 236 nm

3,3.5.2 .CALCULATION OP i\tAx VALUES POR SUBSTITUTED AROMATIC ALDEHYDES,

CARBOXYLIC ACIDS AND ESTERS
fheAmax(nm) values pertaining to the principal band

KETONES,
transition) ofsubstituted benzene derivatives
(ArCORIArCHO/ArCOOH/ArCOOR) can be predicted by using the data given in the Table 3.13.
The A.max values for 6-methoxytetralone (a), 3-carbethoxy-4-methyl-5-chloro-8-hydroxytetralone (b)
0 Parent ketone = 202 nm a~d 3,4-dimethoxy-4b,5,6,7,8,8a, 9, IO octahydrophenanthren-10-one (c) can be calculated as
Double bond extending conjugation = 30nm described below: _
= 12 nrn
-
One ~substituent
One y & one ~substituent = 36 nrn +3
(a) +25 ;t~H = 246 (parent)
Exocyclic double bond = 5 nrn
....
· CH30 +3 (o-ring residue)
COOH Cale. •Amax= 285 nrn
1 + 25 (p-OMe)
(i --
3.3.S Absorption due to aromatic compounds
Cale. A.max= 274 nm
0
Obs. A.max= 276 nm
3.3.5.1 BENZENOID AROMATIC STYSTEMS
The ultraviolet spectrum of most aromatic compounds consists of three absorption bands, all due to Cl
re- ,tt, transitions. In the case of benzene, an intense band, without any vibrational structure, occurs (b) A.~H = 246 {parent)
at 184 nm (E = 60000) and results from an allowed transition. The weaker bands at 204 (£ = 7900) + 3 (o-ring residue)
and 256 (E = 200) result from forbidden transitions in the highly symmetrical ~nzene molecule, the + 7 (o-OH)
band exhibiting characteristic vibrational structure as shown in the Fig. 3.14. ,
The band at 256 nm, sometimes called the bcnzenoid band, is usually easily identifiable. It has Cale. = 256 nm
OH 0 Obs.= 257 nm
almost the same intensity (E = 250 - 300) and similar vibrational structure (upto six vibrational
(c) OCH3
bands) in benzene and its simple derivatives. The vibrational structure is less evident in polar solvents
and more sharply defined in vapour spectra or in non-polar solvents. A.~H = 246 (Parent)
+ 3 (o-ring residue)
s ,--------, I'• l + 7 (m-OCH3)
+ 25 (p-OCH3)
3 Cale.= 281 run
!' 2 Obs..= 278 nm
\'
01 I l l3. B.A. Braude "Ultraviolet and Visible Light Absorption in Determi~atio~ of Organic Structures by Physical
180 Methods", Now York: Academic 1955, Chapter 4. pp. 171-194.
·).(nm) 280 • 14, B.A, Braude, "Ultra-violet light Absorption and the structure of organic Compounds''. Ann. Rep. Progress
1-1&, 3.14 The ultravloltt spectrum or benune In hexane Chem. Chemical Society of London, XLII, 105-130 (1945).
15• A. Buraway, Bcrichte, 63, 3155 (1930): J. Chem. Soc. 1177 (1939).
.t... t,
 -
Ut.TltAVJrA..l!T SncntoscoPY 1"
--
.,.,.ril,al l,(INI (K
()JlGAJ'IIC
-JS' J.Jl
~~OSC()PY
~pa. I ..~ - -
,.,,.,,,_u"'. .,Mp,;
a.- lralUl!b;;
--
--
_,.,...,,,Ju/IS~,,,. ... _ ,
• - -• - ,.,CoG /bo DOH/
:---::::::::::-::::::::=-----------------------
...-.;,=· -·-. •• •• -
·-•-• ••., -;;J
-- --
A~ompou_ ,uh
azo-grouP •• an!Jog'!Us to the ethylenic link.a~ wifh two <7bonc& being replaced by rwo lone
.,, of electfoM (-N~N-). The band Pfflaining 1o trwftioll ilt sadl c.ompoalds ia
~.,..,a10,,..COOWArC()OR A - --..
:;: far (vacuum) ultraviolet reg.ion. The,.-,. ,re transition in alfpha6c az:o compounds appears as•
...... - - .... -Coll, - 246
'""1
_.eak t,and ('-a<~ near 3SO nm while trans.-~ben-z.ene ab1orbs ar 320 nm (i-_ =- 21000).
250 ~ b l e absorp(ion for trans-stifbene occun • 29S nm ( e_ ,. 'lNY.,'1),.
G • .-Jkyl « - - (,..COR) - 23o
G • H. (AJCffO)
G • Off. OR. (AtCOOH .t: ArCOOR) 3 J.6.2 Q)MPOUHDS COHTAOOMQ .MLUlPLE ao.-,om SRt,"l.rfft,-..
Jnc,r,,,n,l fer w,rio,a s,,bstilWfllS Oft Ar. o.m +3 (ibiafteS• Tbion-esters, sulphoxides and sulphoue1)
p + 10
(i) A0cyl oc nng residue
(ii) -Cl

o. m
p
o.m

+o
+ 10
+2
,, ,,...,,
'fbe ,weak 71,, - ·-------
., -..Anes and Thionesten
n - ...,_,.
c=o groups- The absorption
of _c = s group appear .t mucJa longa wnelengihs tfaaa lfx.e of
as sh,fted to 5borter wave1engm mmionesren and is c1aea. a::coo,penw.:ct
(iii) -Br p +Is 6
o, m +7 1,y ·an inteme tr-+ft- band' • This is illustnted by the following examples:
(rv) -OH.-OCff,--OR p +25
0 +11 ~s ,l_{nm) =49S (weak)
(v) -0- (oxyanion) m +20
p + 7g. eyclohexane thione
o,m
p
+ 13
+S8
Cff3-i-O-C2Hs .A_(nm) = 2-41 (c_ = 8100)
(vi) -""H2
o. m +20 s
(vii) -"'HCOCH1 p t4S EdJylduoarel4te 369 (c_ = 18)
p +73
(viii) -llo'HOl1 o. m +20 (ii) Sulphoxides and sulphones
(ix) -N(Ol.vi p +85 'J'bc n pertaining to S=O group in saturalcd sulpboxidc ap,~s near- 220 mn(~ - 1500)
and undergoes a hypsochromic shift with increase of solveu polarity. Aromatic sulph(mdes display
. -This value may be decreased martedJy by steric bindrance IO planarity. an inaense K-band in addition to the displaced B-band.
0
3.3.6 Compounds containing multiple-bonded nitrogen and or sulphur
3.3.6.1 CoMl'ouNos CONTAINING MULTIPLE-BONDED NllllOGEN (IMINES, NTl1ULES AND
In compounds containing the grouping -1-x.
the position of a ~ buld ..tcpcoos 011
the clectronegativity of X; the greater the ~lecbooegativity. the shorter will be the wa:wdcngth ol
AZO<OMPOUNDS) absorptic,n.
(i} /mines and nitrila Salpboaes
The absorpCioa maxima of compounds containing unconjugated C = N (imines) or OEN (nitrites)
Dialkyl sulpbones arc transparent through the ultraviolet region. In strongly alkaline solutioo. these
,roupinp generally occur below 200 am. Conjugation moves the absorption to higher wavelengths
sulphones give rise to some absorption as a result of anion fonnatiolL11
(just inside the near UV region - 210 nm) but lbe raulting compounds tend to absorb at somev.ilal
When the sulpbone group is attached to a carboo-carboo double bood. absorptioo pcruining ID the
lborta wa~gdl than 1beir carbon analogues. as illustrated by the following examples:
double bond becomes stronger than that for olefins. This is due to the iotcnctioo bcrwecn the double
o.,,o,,,,d A_nm (t;.J bond and the sulpbone group.
01,cH=-CH-Cll==NC.U. 220 (23000) la aryl alkyl sulpboncs. the primary and sccoodary absorptioo maxima vc shifted by IS nm or
Cl,cH=-CH-CH:sCHCII, '227 (23000) towards longer wavelengths. The intensities are also ioC'rcascd..
_la diaryl sulpboncs. the primary absorption band is again shifted toward )oQgcr wavelength reLati~
lo the correspooding band in phenyl methyl sulphoncs (Table 3. 14)-
0-C=N 211 (11200)
Q-cem 223 (12500) l6. M.J. Janssen. Rec. Trav. Chem.. 79 (1960) 45-l. 461..
l7. C.C. Price and S. Sulphur bonding. Ronald. New Yort. 1962.
 (
-- ULTRAVIOLET SPECTROSCOPY 157
156 ORGANIC SPECTROSCOPY 3.J6 Absorption ma.dma of l<»M common I.wthiocyanates (R-N=C=S)
Table 3.14 Absorption ,,.axima of some sr,lphones
Primary band- Secondary band ll Amn(nm) loge
, __,. Ina:£ l , __
Compounds A,n.,.\nm, --.,. - ~ax.\"
• m) log t t.fethyl 2.8
2Jt
U4
204 •• 3:87 2S4 __ Ethyl 24S 2.9
Benzene 217
JsoproPYI 246 2.9
3.83 264 •> 2 ,.Butyl
Pbenylmelhyl,ulphonC 4.2 248 3.0S
235 266 3·~1 Phenyl
Diphenyl sulphone 238 4.2 3• 269 4.08
279
4.08
---
p-Hydroxyphcnyl methyl sulphone 236 41 262 ,
1 ,03 Z79
Di-p-hydroxyphenyl sutphone •' • ; 4.30 a-Naphthyl 310 4.26
326 4.20
3.3.6.3 CoMP()UNOS CONTAINING MULTIPLE-BONDED NITROGEN AND OXYGEN ,i· 1 '. • ., JJ-Naphthyl 26S 4.45
The groups containing nitrogen-oxygen ~ultiple _bonds, n~mely nitro, nitroso, ~i!1'ate and nitrites, 29S 4.20
exhibit weak absorption i_n the n~ ultraviolet region -~ult~ng from n trans1u~ns. Some of the 30S 4.20
groups can conjugate with olefimc double_ ~nds_ g1vmg intense n~ absorptions. Absorption . .
maxima of some common compounds contammg mtrogen-oxygen multiple bonds are depicted in the ( ii) Thioureas
The UV spectrum of thiourca, in the range from 190 to 380 n~ is characterized by two high intensity
Table 3.15. • • ' maxima at 194 and 235 nm and a low intensity band20 appearing as a shoulder at - 278 nm.
Table 3.15 Absorption of some common compounds containing nitrog~n-oxygen linkages The examination of UV spectra of thiourca in aqueous solution at different concentrations (0.01
to o.OOlM) reveals that the molar extinction coefficient at l_. = 235 nm is fairly insensitive to
Compound (solvent) A.mu(run) (Emu) concentration. This indicates the absence of tautomcric conversion.
The position of the major absorption band in many thiourcas have been reported by Kjaer et al20
27S (15)
Nitrobenzene (heptane}
237• (9500) and by Gosavi and Rao21 . The absorption maxima of some common substituted tbioureas are depicted
Niuobenzene (alkali) '
229• (9400) in the Table 3.17.
J-Nitto-1-propcnc (ethanol)
( 23S• ,,. , •;,' i;fl i • ·, (9800)
300 (100) Table 3.17 Absorption maxima for sorM common substiluled thiourras
Niuosobutaoe (ctbcr) f ! (, '
. 1,. 665" (20)
Octylnitrale (pcotane)
t.
270.. -
.I t ,,-!
(22) Compound· .A_.(DID) log E
n-Butylnittile (ethanol) 218 (1050)
H2NCSNH2 278 (s) 2
313-384••·
23S 4.05
... lnnlilioa' . ,,•,! .,! • ··,,:'. 194 4.24
. ••k is typically a point of inflection in the spectJa of nitrates. .-1 I f L !' I
Mc2NCSNH2 285 (s)
••--rim region is one of fine structure with bands roughly 10 mm apart. 243 4.14
McNHCSNHMc 280 (s)
'' 238 4.13
3.3~.4' , ColaouNos CX>Nl'AINING MUU'IPLE•BONDED NITROGEN AND SULPHUR Mc2NCSNHMe 2SO (s)
(laodliocyamta aad thioureu) ,'1 . ' \ ' ·' I • ":} J
240
' t.y,; • }
4.14
iJ '•? ~f:' •.,: :.:Jtj p 1]fr;l;.,u·. ,, n
·.1_;. ! • ••. • ,- ,' .J < • ·•~:~. ' • •.
210 4.12
(lJ-~(R,.,N,, C.S),,i,,,: ·. • 1' •: ; , • Mc2NCSMe2 305 (s)
. · • . ·. , ',I' 2
1be ultraviolet tpeClrUm of alkylisothiocyanates arc characterized by a single absorption b8:°d of 256 4.24
mecfl.mt i..,_,, (e. 1000) ..ia-fhe ~ge from 248 to 244 run18• A!'omatic isothiocyanates d1sp~a~ 209 3.79
man, complex apecbadue to the pca1nccof the aromatic cbromophorc. They e~ibit strong absorptto
••shoulder
ia,_nsi9,n..bc&w1 •;50-330.-am,(....U y MC>ve 300 nm). often associated with fine strUcture,
19
Tbe ablorpdon rn•:Jima of JOme ~ l e are given in the Table 3.16. 3 •3.7 Substlt~tlon of benzene by auxochrom•s. chromophores or fused rings:
3•3 ,7 .1. (i) Alkyl substitution: Alkyl su~titution on benzene
ring produces a bathochromic shift of the
18. B. SVIIICk, R. Zlbradnlk IDd A. Kjaer, Acta Olan. &and., U (1959) 442. , , . , . 1. •
19. R. Zllndnik. D. Vlachova and J. Koutceky. Coll~on ~Clem.Commu n., 27 (1962) 2336, A, Kjacr, R. Zahradnik, K. Dusek and J, Khabam, Acta Chem. Scands.. 16 (1962) 2041.
' R.k. Oosavi and C.N.R. Rao. Can. J. Chem. 48 (1967) 1897.
.1..
J I ii -- -- -- -- -- -- -- -- --
-
/ 175
ULTR AVIO te·r SrECTROSCOPY
i
cnrbon orbita l of the carbonyl group with a
shift t,eca~sc of th e overlapping of the nntibom.ling
group .
vacant orbital (usually 3s) of the electronegative
l)dermination of co11figuratio11
tion of configurational correlation.
Ultraviolet spectroscopy has been used extensively for the determina
This is illustrated by the following examples:
gues, both the absorption maxima and
(i) In conjugat~d syste ms such as biphenyls and analo
the molecules are twisted around the
extinction co-efficae~ts are affected in a predictable manner as
, the UV spectra of simp le biphenyl
pivotal ,bo~ds frolT_l _a plana r to a non-planar conformation. Thus
0) and 224 nm ( Emax =700), respectively.
and 2,2 -d1methylbiphenyl exhib it Amax 252 nm ( Emax = 1900
in the latter are due to steric inhibition
The hypsochromic shift and decrease of extinction coefficient
of resonance indic ating non-p lanar configuration.
t in a reduction of orbital overl ap with
(ii) Any non-p lanar arran geme nt of double bonds will resul
ased intensity. This is illustrated by
a corresponding shift of Amax to lower wavelength and decre
in which there is little conjugation betw een
taking the example of 2,3-d i-tert -buty l-l, 3-butadiene (I)
This comp ound exhibits Amax= 180 nm and
the double bond s, due to the bulk of the tert-butyl groups.
diene exhibits Amax = 227 nm.
a shoulder at 220 nm wher eas a typical dialkyl-1,3-buta

Sample Problems
ion.
Q. 1. What happe ns when a molecule absorbs ultraviolet radiat
molec ule result s in electr onic transitions, promotion of electrons
Sol. Absorption of ultraviolet light by a
excited state orbitals (40-70 kcal/mol).
from low energy ground state orbitals to higher energy
the following compounds (i) Cyclopentene
Q. 2. Define chrom ophor e and identify chromophoric group in
(ii) Toluene (iii) Butanone (iv) Methanethiol (CH3SH).
electronic absorption. The chromophoric
Sol. A chromophore is a functional group which is responsible for
groups present in the four compounds are:
(i) >C=C< (ii) C6Hr (iii) C=O and (iv) -S- •
mittance (iii) Absorption maximum (iv)
Q. 3. Define and expla in the following: (i) Absorbance (ii) Trans
Mola r extinction coefficient.
Sol. (i) Absorbance A (optical density)
of the intensities of the incident light and
The absorbance A for a material is the logarithm of the ratio
value of which can be calculated from the
the transmitted light: It is a dimensionless quantity, the
on (c) and the path length (I} through the
molar absorption co-efficient (£), the molar concentrati
material, according to the equation;
A = log 1ofc// = £ cl
.
(ii) Transmittance y transn utted hy a subst ance to the
mater ial is the ratio of the radian t energ
The transmittance for a relatio n.
by the following
radiant energy incident upon the substance and is given
 176 ORGANIC SPECTROSCOPY
(iii) Absorption
Absorption maximum
maximum (~.)
is a discernible

T • 1/1
0
wavelength at
which an electronic transition occurs. At l

----.__
--- ULTRAVIOLeT SPECTROSCOP Y
often, merge (due to .solvent:solutc interaction) to give a broad absorption band, when spectral

t 77
of the energy levels of the orbitals concerned, a traMition between these levels, when gaseous sample
Is irradiated gives rise to fine structure consisting of a number of closely, spaced Jines which, very
ab,o,bance A (optical denSity) follows an exponential law (Beer-Lambert law) of the form,·-..., 11i, measurements arc earned out an solution.
Q. 10. Antibonding orbitals are described by the symbols ct- and ,,_,. and not by n•. Expalin.
Ac log ([JI)= sci Since n electrons arc not engaged in bonding there are no corresponding antibonding (n•) orbitals.
Sol.
Q. 11. Acrolcin (CH2=CHCHO) absorbs at 217nm (Emu= 16000). What is the weight concentration (g/ml)
A )., the molar extinction coefficient is expressed as Emax·
required to observe an absorbance of 0.8 when the cell length is I cm?
(•t) M~iar extinction coefficient (£.nu) ..,.ulc's probability of absorbing a photon.at lor Sol. The molar concentration required:
iv • • lated to the mo1...... · h mtens1
• ·ty ab sorptton
· ·~
M0 lar extinction coefficient is re fi 10• arc termed hag Whil C=Ale I= 0.8/(16000 x I]
• cd lcculcs Values or £..,. , • . cd) c
to the intensity of ex~,t • ions (units for Emax arc generally onutt • . \ = 5 X· 10-5 mol/litre
values < 10' arc low mtens~ty abs~~ iblc in the following compounds: Molecular weight = 56.06
Predict the various electronic ~s1t10ns poss .
Q.4. Weight concentration required mol/litre =(5 x to-5 moles/litre) (56.06g/mole) (le>3ml/1itre)
Sol.
(i) CH. (ii) CH1Cl (iii) H2C=O (iv) Cl1
(i) 0-
= 2.8 X 10~ g/ml.
Q.12. For a solution of camphor in hexane in a IO cm cell, A at 295 nm was found to be 2.52. What is the
(ii) a-. a-
(iii) a-, a-, ,r concentration of camphor?
n - ,,_,.
(iv) a- a-
Q. s. Whal do you understand by singlet and triplet state of a molecule? Whi.·ch state has the ·1owcr energy
and why! • • w1"th or w1"thout h
• exc1tauon
Sol. Singlel and triplet stalCS arc the result of electronic c angc o f spm.
. Increasc 0
in multiplicil)' leads ro lower energy in the triplet state.
-
Q." How will )'OU account for the variations in ultraviolet absorption for the following compounds?
(i) A_ for medaanc • 125 nm •
Camphor
(Ii) A_ for edlane • 135 nm •
(iii) A_ for c,closausrme • 190 DID ce::. =
[).,,,.,.--=295 nm 14)]
Sol. A.,.,..iy all lbe dne compounds contain only the er-bonds. In methane only one transition is A= eel
anolWICI i.e.. for C-H band. In ethane two tnasitiom are hm>lved. ane for C-H bond and second for =
2.52 14 X C X 10
lbe C-C bGDll C-C band lralitioa requires leu eDelQ Oaqer wayelqth) than for a C-H bond. c = 2.52/14 x 10 = 1.8 x 10-2 moles/litre
C-Cbondl i n ~ are DOt pare abonda bul~',!litial and c:onsequendy What is an auxochrome? Explain how an auxochrome exerts a bathochromic shift on a chromophore
sequila llill lea CDellY (laapr WDelea&lb) f a r ~ - ' " • .•bc>a4 • ' ... . . such as an ethylcnic bond.
Q.1. Explain lbe vmildaa ia lbe vllaecf A.afar An auxochrome is an auxilllary group which interacts with the chromophorc causing a balhochromic
shift. Typical examples arc: -NH1, -OH, -F and -Cl.
. T h e ~ electrons on the hctero-atom of the auxochrome become part of an extended 1r system
by lntenctina with the ff-electrons of the olefinic system. This interaction has the effect of lowering
the encqy, both of the ff and n"' orbitals and consequently the ,r n:- energy gap decreases resulting
CH,l.~•-258 mn , •in rqcl-atft.
Sol.
11 Transition occun i n ~ c:ompoomda On - ; , . . ·down in die group from Cl to Br to~ Sugut an explanation in terms of orbitals for the fact that azobenzene is a deep orange-red compound
lhc n elearons are found in higher priacipa1 eDellY lewis (principal quantum numbers are 3, while hydrazobenzeno is colourless.
respectively). These electrons. beina far away from the allrlctlve force of the nucleus, are more4 eastly Azobonzene. ;-N-N-f ( d i • uans> bas the cbromopbore conjuaated wilb both the rings. The long
Q.I excited and COIISequendy lbe absorpti°" m.-,ghnum occurs at a higher value. wavelength absorption is n .- at 440 nm (k 500) &ivina riae ID the colour and•-+_. bands appear
Sol. What is an ultraviolet spectrum? Give various regiom Msociated with ultraviolet spectrum. . at 320 and 230 nm (B > 10"). Hyclruobenzene. f-NHNH-f SMUld baw a specllmll similar ID tbal of
~violet lpeClrwn is limply a plot of wavelenath of light absorbed versus the ab~o~oo aniline (~Hi) for which the longest waveleaadl bwl Is ll 280 am. since Ibo two Pi! 1 pair orbitals
~ t yW&Yelencth
against (nm). smittance) and is CODveniently recorded by plotting
(absolbanceoflran molar absorpuvity (e) on nitrogen are approximately It right anal• to one - - • · •
. Q.1s. Define the terms bathochromlc shift and
bypsoc:hlomic sllift. Wbll IINl:tllnl re..e IDQ procllla: a
1:"e ultraviolet ll)eCtnun 111ay be divided into the follOWing regions. bathochromic or a hypsochromic shift in an cqanic: compound
reg,on
<•> C380-780
~• (or Yaeuum) nm).
ultraviolet 0~200 nm) (ii) Near or Quartz ultraviolet (200-380 nm) and visible
Sol. A bathochromic shift (red shift) may be cauaed by a dalD&e a l _ . _ • II, die pnactM:C of•
Q.9.
Sol. Electronic absorption band$ arc .
Electronic spectra arise fJ01n C ~ y broad u COlllpared to mfrared. Explain. .
auxochrome. A hypsochromic shift (blue shift) may occur by
· changes like removal of conjugation.
•~of-•• • •by acb saw:llnl
both vibrational and rotational~~ between electronic energy levels accompanied by change~ 0
.
1
Q.1,.
Sol.
Explain why butadienc exhibits a highor value of A.a. ._._._of..._,..__
In butadiene, the excitation occurs from highest occupied molelwlar odlltal (,w ID diia lowest want
• •nee the wavelength of absorption is a measure of the separauon
molecular orbital (~3). Since the cnel'I)' difforooco for lhis lrWitioa ia lealba tbe 11 na, dUftawc
.for the transition in ethylene, for butadieno (217 nm) is IIMler tbaa 1bal lbr elbyte. (110 ma).
 --- --- ---
absorbed.
S CTROSCOPY . . e an d what is the co lou r
178 ORGANIC PE for the ora ng e co lou r of carrots, has cfc.,
g. .
arotene absorbs in the VIS lble ran the sp tru m (A _: :: 452
ec
•
is the pri nci pal co mp ou nd res rn s~ b! :le region of as the nu mb er of the COnillb.~
Q.17. Explam why f; h bo ds and absorbs light in t e v1s1 decreases
lig ht """'
Sol. P.C aro ten e w I
HO MO and LU M ~s to the en erg y of visible
e between the

, ,
conjugated doubledilT:renc hc ~~ :a lu es of 294 an
d 274 run
an d co nse qu en tly the .d Ete1r
~~ as es• omers of stil be ne fro m
be caleus e! n;"ge
s ometn•c is

~· Ideub
do
8. ntify the

HA
He
HA
'C=C/ ; ' C= C
'H s

cis-Stilbene trans-Stilbene

1elte cgthoplan 4 nm
27ces com
sar)yasfor conjug
l red
fulpa thne~
to atio
p c· - ne
1 arity
SoL
cis isomer, pre ven ts com
The steric strain in• the
• r absorbs
. at.shorte
.
veum
r waim en Am"m .a= u29- 4 nm).
iso me the vis ibl e spectrum. The
consequently the as- nc:
E 30 0) (the red en d
of
of ~11Juga11on is r wo uld yo u predict azulen
ei
Q. 19 . isomer in which the efl'.ect . nm (E -- 400().). Wha t co lou
n IJlllXJmum
urs at
at 7~
3 nm
rtene
Azule
sho hasvel
st wa lra11o
absthorp
aneng nsition occ
exhibit

AzuJene
Wilt
Sol • • . .
Q. 20 . Blue •
305 nm an d m eth an ol
sh ow s Arm,.= 307 nm...
d in hex ane exh ibi ts A.. .x =
An organic compoun nsition?
should be the nature of tra tic of X- transinoo.J'
Sol.
eng th wi th mo re po lar solvent is the characteris len gth and n
Q. 2L 1be shift to longer wavel shi fts the ,r r transition to lon ge r wa've 4 tti
a polar solven t usu all y
Explain why&h vel eng th.
lransition to oner wa the polar so 'dll
Sol.
rge sep ara tio n in the ex cit ed state an d 1
In mo st ,r r transitions,
there are mo re cha
s, sta bil ize s it mo re str on gly than it do es ~
bonding •interaction ground·
by dipole-dipole and hydrogen the excited state is decreased more than that of the . ;
rgy of
&round llale. Thus, thetoene low er ene rgy (lo ng er wavelength, red shift).
shifting lhc transition d the po lar solvents mi0dll
r tra nsi tio ns, the gro und state is more po lar an
ed stale. :1'us.t,.':t
However, in most 11
ele ctr on pa irs in the gro und state than in the ex cit wavelen.,ih (
red r
JDOre_ ~g ly _with unsha
ft).tioo FeqWres more energy and consequently the ab
sorption occurs at a sho rte
shinsl
lra
Q.. 22. dic medium. Explain.. "'
in neu tral medium to 203 nm in aci
Sol. fro m 0 nm
-1... for aniline shifts in aniline ~c ~r s at 230 nm because the pa ir of ele
23 ctrons on th en ~
n II'
1be ~p tio !' ma_ximu ?'
nn g. In aci dic me diu m, however, ab ption occurs 81
sor
the aromatic pa ir electrons
atom 1s 1n CORJugation wuh is is due to the remova) of cortjugation of the Jone 0
(• 203 nm ). Th
wavelength of aniline with the ,r bond system of the ben zen e ring.
Q.23. nitrogen atomthe diene (I) ia absorbed at lower nm than (II )
Why A,... for
 ~--- ---_ -_---- ------ ------ ~~~~ ::.::::
ULTRAVIOLET SPECTROSCOPY 179
..:::.:. :::=-: ...:.... .-
CH-CH

I
II
In both ~e dienes, there are four ring residues as substitucnts. In diene (II), the two double bonds arc
exocy~hc and c~nsequently, ~he ~u for II will be higher by 2 x 5 = 10 nm.
[)escnbe the vanous absorption bands exhibited by saturated ketones and aldehydes.
Saturated ketones aldehydes display three absorption bands,
(i) A tc transit1on absorbs strongly near 170 nm (K-band).
(ii) An n transition absorbs near 190 nm.
(iii) An n transition absorbs near 270-300 nm (R-band).
The R band ts weak (£max< 30) and results from the forbidden transition of a Joosely held n electron
to ,rt, orbit~, the _lowest unoccupied orbital of the carbonyl group. The most intense band for these
compounds 1s always due to the ,c rt:"' transition (K-band).
Q.25. Biphenyl exhibits a very intense absorption band (Emu= 19000) at 252 nm but its 2,2'-dimethyl
derivative shows absorption almost similar to o--xylene (Amax 262, En.ax 270) Explain.
Sol. Since the angle of twist in biphenyl is small, therefore, conjugation between the rings is not aff~
Biphenyl thus shows a very intense absorption band at 252 nm (K-band). 2,2'-Dimethylbiphenyl with
methyl substituents in ortho-positions, however, is more stable in twisted conformations as compared
to biphenyl and suffers serious non-bonded compressions from the juxtaposed substituents. Thus, 2,2'-
dimethylbiphenyl may be regarded as two molecules of o-xylene and shows absorption similar too-
xylene, due to loss of conjugation in the twisted conformation.
Q.2'. Acetone absorbs at 279 nm in hexane whereas the value of Amax in water is 264.5 run. Expalia
Sol. The blue shift results from hydrogen bonding, which lowers the energy of the n-orbitals.
Q.27. Suggest a reaso~ for the indicate~ differences between the absorption maximum of ortho- and para-
methyl acetophenone.

COCH3 COCH3

CH3
Amu = 252 nm (E= 15800) = 243 nm (E = 9500)

The ortho-methyl group twists the carbonyl group out of conjugation with the aromatic ring.
How can the structures I and II be decided from their UV spectral data pertaining to K-band. [A.au=
296 run (finax = 10,700) and Amax= 281 nm (£max= 20,800)].

I II

The ,true..·· ·.th 1 = 296 nm has almost one half the intensity i.e.,~= 10. 700 of K-band than
lbe other 1U1C WI "'snax • • h
compound. This decrease in intensity 1 f
1st~ res~ lo stcnc• h. dran
dtn. cc by met!'yl ~ps and
ita effect on the absorption of conjugated systems. us t e compoun with decreased tnteDS1ty of the
K-band is I.
 ··~ I
'"' .
tF C ur 1J G 1, -- - ..--Tfns is ca 1l ca tri n! annur\t
in this apparentlyn)io-orbitals of th e he tero-atom
ax-" and p(
The higher valueofofthAm oup .
So l of the .,-orbital e C--v gr
ui sh be tw een eq uatorial and axial confonn atton
n. can be used to disting
conjugatiovio op y
How uJua let spectrosc
depicted below: Br
Q. JO.
ff

o-- II

ketones_ is influenced
by the
of a, P- D ?s at urat ~d
(i.e. R-band) the R-band to
The longer wavelength
n
e e~ ec ! of an a,u aJ subsbtuent to d1_splace
Sol. p in the )'position.. Th
presence of a polar grou eater than the equatonal isomer. hibit a h·g1h
longer wavelength being
gr
ular fo nn ul a C ," 6O whose UV spectra ex
mol ec
mers possible with the at AmaX = 280 nm.
Q. 31.· Write all the iso n.x 187 run and a very low intensity peak
= coholic, ether, aldchyd·
inten sity pe ak at A. cates that the co m po un d co ntair~s al
there arc
Th e pr es ence of single oxygen atom indi lacks four hydrogens from being saturated-
SoL e molecular formula s, one double
or ketonic grouping. Th rings, two double bond
Consequently the system co ntai ns tw o
e unconjugated C O. =
Thus, the
degrees of unsaturation. rptio n co in cide s w ith th
one triple bond. The abso
bond and one ring or are :
various possibilities
0
=O
C = C H -C H 2 -C H
~ ~ - f f H2

benzene.
Q .3 2. ib e th~ ~a rio us ab so rp tion bands exhibiled by
~s cr peak.
Give the ong1n of each
absorption bands·
Sol • Benzene displays three
(~? Ainu =184 nm (Emu
=60, 000); E1 b~ d
or K band
u= 79,000);
C~g l.n.x =.204 nm (E m =200) ; B ba nd
(in) Amax =256 nm (Emu re
..
sults from an allow d t~ sn io n, w~ereas the weaker bands near 200
ba nd ne ar 18 0 nm
The intense forbidden transitions in
th chi
al benzene moJecuJe.
and 260 nm result from inate from ,r ,r- tran .1. e g Y symmetnc
AJJ the threbe e bands orig s1 ions. n ne
Q .3 3. :nu f th
en o1
.d
ba nd sh ifts to wa rd lo ng er wavele
gt b .as the nu m be r of linearly fused benzt
2
e nz ,
.
nngs increases. Explain en ergy ga p be twee
Sol. nu m ber of tr-or bital s increa se s, the
i - n H O M O and LUMO goes on decreaseringof
As the
n.x for the benzenoid band shit ts toward longer wavelength as the numb
and consequently the A.rings increases.
Jine~ly f~~ed benzene nced .
is not observed in o- or
m-isomer.
Q. 34 . N itroa n, hne ex hi bi ts in the K-band a pronou red sh ift w hich
p-
Explain. .