Ch 14 IR :

spectroscopy
IRS allows for identification of functional groups by radiation causing vibrational
transitions of bonds called
"
G bends
"

scissoring 4 twisting
"
"
stretches a-
.

Vibrational Modes of a Bond

n= 5
-

-
n = 4

n =3
-

alcohol

. absorb
rHow energy
n -
-
O

EI to left
energy 4 frequency radiation
o o
right
*
stretching a bond must change
the dipole moment of a molecule o
bonds w/ higher polarity =

higher absorption
in order for bond to be IR active
partial Farge
Dipole Moment =
M = S °
d ←
distance of separation

IR -

Inactive Bonds

r
. =

g. = O
F E
trans 4 no dipole
when stretched ,
it

will still O no light absorbed

-
-

SP n 3300
⇐ sp
g

I 50% s character
↳ shorter bonds stronger
=
=

I
" H ←
> 3000
s
✓
33% character orbital lower
energy 4 closer
orbital s * s is in
hybrid
\
to nucleolus than p orbital
L 3000
"" ← S orbital
25% s character a higher energy
-

*
higher frequency = shorter wavelength

you go to left higher energy higher stretching stronger bonds

*
as = =
wave =

be stronger bond needs more

energy to make it vibrate
3 Things to look for In IR

1) Wavenumber =
energy of IR absorbance

G depends bond strength 4 masses

on ass mass to
frequency T
of atoms bonded together as bond strength 9 frequency T

Absorbance Trends
"
1500cm 1500cm below fingerprint
"
t A
diagnostic region →
region
-

functional group9 F
identify unique to molecule

o
Hybridization : S vs p character affects IR vibration

more s character =
shorter , stronger bond
°
Resonance in C =
O ( carbonyl compounds) →
weakens bond =
lower wave number

ketone Aldehyde CarbonIic Acid Ester Amide

'" R
pi
"
#
'
-
or
.
a.
p, ~2710
H p, o soo
3500
r .
r
ly
R3
n

~ 2810

0%48
oufrone-OQ.SI .
I
'

aldehyde very polar

=
strong -
p /
ketone ? absorbance
1710
⑥
~

EO bond
O l
→
C O
-

-
-

carbon Iic acid w/ resonance If it has a single bond

,

character it weakens,

o .

' C -
H
sp
①
-

C O O
- -
-
 TH IT , single ,
IT

conjugation lowers C =
0
Stretching frequency *
only in carbonyl
"

Oj Ogi O 09
:

16 a ,
n
1674
& ll
-

~ 1718 - ll n 1695 11
^
N AT MHz
(2 resonance) ( 3 total resonance) (3 resonance ,
2 have double bond)

2) Intensity =
how much is absorbed at that wave number small
of
µ
-

,a
.ge.

depends on bond dipole =

how big is the peak ?

°
In symmetrical
a alkene it would not show absorbance bc it is non -

polar
0
Dipole is needed for absorbance

o
Intensity also depends on # of bonds of a given type
more double bonds =
stronger absorbance

3) Shape =
sharp or broad peak °
mainly O H-

bonds

depends on homogeneity of bond →

more homogeneous =
sharper peak

✓
←
broad signal be of H bonding It makes bonds weaker
-

so at absorbance the broad signal is be some bonds are

strong 4 others are weaker
molecules bumping into each other

✓
←
narrow signal =
no bombing into each other
vibrate at natural peak

Hydrogen Deficiency Index ( HDI) :

degrees of on saturation

If given just molecular formula ,

HDI allows you to calculate how
many hydrogens
are missing from the total saturated possible structure

unsaturated
alkene I
°
Cs Hn Cs tho =
of saturation
~\ ne
each reduces # of
degree
saturated missing 2 H molecule
two
=

has double bond

H by
each degree
ring one
:
 effect HDI as It
halogens X same on
= =

HDI 112
oxygen does not affect nitrogen increases HDI by

HDI = E ( 2C + 2 + N -

H -

X)

ex . What is the HDI for CsHoo Br N ? I ( 215) -12+1 -

8 -

l)
=
2

* You can figure out a molecular structure from combination of

IR ,
mass spec 4 HDI

Practice Problem
•
Explain how you will use IR spectroscopy to monitor the progress of the rxn :

⑧ HO
i
CHsCHzMgBr V
II
.

→
N z .
Hao NV
lose C=O To gain C -

OH
this not important

*
looking at IR page we can say : the 1680 1750 peak will disapear 4 a 3200 3600 -
-

will apear ( O H) Narrow ( C O) peak will dlsapear 4 broader (O H) will apear

-

.
-
-
-

Which of the consistent withe IR spectrum ?

following compounds is
following
•

C OH
-

O C C
-
-

O
4650

I
1500
C-
OH
-

Cy "
O ⇐
II l
OH
H
F
X X X X X
l l l l l l l l l l
V V V V V
l l l
OH C OH
-
-0 OH OH

(=C :
weak C = O :
 Wiley Ch 14
•
Calculate degree of onsaturation for following molecular formula :

Cs H lo Or ←
Oxygen has no effect bc does not remove Hydogens
A
,
Missing 2ft =
I degree of unsaturation

•
Which 2 compounds have same degree of un saturation ?

Cs Huo O

Cs Hall Or I
Cs Ha Nk E ( 512) -12+1 -
9 -
O) = I 113 -
9) = 2

Cs Hio I
⇐
Rank each bond by increasing wavenumber

32,88; 1,998 333% 30,88 1,488 229%0

- -
-
-

I > 3 7 5 77 > 2 7 6 74

*
Frequency is not directionally proportional to
wavelength