UV-VIS Pre-reading question

When discussing UV-VIS spectroscopy, conjugation should be considered. It is

important to be able to recognize p-electron systems that are conjugated, as
conjugated systems exhibit different UV-VIS absorbance when compared to
non-conjugated systems.

Question. State whether the molecule contains a conjugated p-system or

not.
3. UV-VIS SPECTROSCOPY
 = ~200 – 400 nm (UV), 400 – 800 nm (VIS)
E = ~150 – 600 kJ mol−1
UV-VIS radiation raises electrons in some molecules
(generally those with p electrons) from lower energy
bonding (or non-bonding) MOs to higher energy anti-
bonding MOs.

max
Compounds containing only -bonds are
generally transparent to UV-VIS light.

All molecules containing a non-conjugated

i) C=C show an absorption at ~170 nm, due to a p - p*
electron transition.

ii) C=O show an extra absorption (weak) at 280 nm,

due to an n - p* electron transition.

Limitation: Doesn’t give any information on the

number of p bonds.
i) C=C (non-conjugated)

E E

ground and possible excited states

p - p*  - *
transitions
 ii) C=O

E
E

ground and possible excited states

n - p* p - p*
transitions
Note: E n → p* < E p → p* so the absorption for
n → p* is at longer  than p → p*.
3.1 Conjugated systems
In conjugated systems E for electron
excitement is smaller.  Absorption is
observed at longer wavelength than for non-
conjugated systems.
max
CH2=CHCH2CH2CH=CH2 172 nm
CH3CH=CHCH=CHCH3 227 nm
CH=CH2 244 nm
CH3 CH3 CH3
CH2OH 326 nm
CH3
CH3
Any molecule containing conjugated double bonds
will show an absorption at >200 nm.
Remember: double bonds that alternate with
single bonds are said to be
“conjugated”.

The greater the number of double bonds in

conjugation the smaller is E and the larger
is the longest wavelength max value.
 3.2 UV-VIS AND BEER’S LAW
The intensity of an absorption is defined by
Absorbance, A = log10(I0/I)
(where Io is incident light, I is transmitted light).

For a particular compound at a specified :

Absorbance  concentration and
path length
The more “effective” a molecule is at absorbing light at
that , the greater the absorbance.
Beer’s Law
At a specified wavelength ()

A=bc
A = absorbance
 = molar absorptivity in L mol−1 cm−1
b = path length in cm
c = concentration in mol L−1
Examples:
max
O 188 nm  = 1400 L mol−1 cm−1
CH3CCH3 279 nm  = 15 L mol−1 cm−1

(CH3)2C=CHCH2CH3
max 180 nm  = 11000 L mol−1 cm−1
O2N
(CH3)2C=NNH NO2 max 344 nm
 = 17000 L mol−1 cm−1
For strongly-absorbing solutes,  is usually in the
range 105- 106 L mol−1 cm−1 so very low
concentrations (~ 10−5 - 10−6 mol L−1) used.
3.2.1 Utility of Beer’s Law
To determine concn of a UV-VIS absorber….
i) Find absorbance at max and substitute into Beer’s
Law if molar absorptivity at max known.
Example: For a solution of camphor in hexane in a 1
cm path length cell, the absorbance at 295 nm is
0.80. The molar absorptivity at 295 nm is
14 L mol−1 cm−1.
What is the concentration of the camphor?

A = 0.80 b = 1 cm  = 14 L mol−1 cm−1

c=? [A = bc]

c= A = 0.8/(14  1) = 5.7  10−2 mol L−1

b
ii) Making a calibration plot for solutions of known
concentration at a specific wavelength.

x
A x
x
x
x
concentration
Then at the same wavelength determine the
absorbance for the solution of unknown
concentration, and read off the concentration from
the calibration plot.
4. MS, UV-VIS and IR and structure
determination
Consider the following:
i) A compound with molecular formula C3H6
DBEs = ½(2n4 + n3 – n1 + 2)
= ½(6 + 0 – 6 + 2) = 1
 one p bond or ring

CH3CH=CH2 alkene
UV p−p* absorptn
cycloalkane
~170 nm
IR C=C absorptn
1680 -1600 cm-1
ii) A compound with molecular formula C5H10
DBE = 1

cycloalkanes or alkenes
CH3CH2CH2CH=CH2
CH3CH2CH=CHCH3
CH3CH=C(CH3)2
CH3CH2C=CH2
CH3
CH3CHCH=CH2
All alkenes have: CH3
UV p−p* absorptn ~170 nm
IR C=C absorptn 1680 -1600 cm-1
iii) A compound with molecular formula C3H8O
DBEs = 0
alcohol
CH3CH2CH2OH CH3CHCH3
OH
IR O-H absorptn 3700 - 3200 cm-1
[C-O absorptn 1250 -1050 cm-1]

ether
CH3CH2OCH3
IR [C-O absorptn 1250 -1050 cm-1]
No O-H absorptn.
→ Conclusion:
MS, UV-VIS and IR give
NO INFORMATION
with respect to the HYDROCARBON
SKELETON.