Chp. 5 Spectroscopy

Spectroscopy
Infrared (IR) Spectroscopy

IR spectroscopy is one tool we use to determine molecules’ structures. IR
spectroscopy works because all bonds wiggle in different ways when you shoot IR
light at them:
bond stretching bond bending
These bonds wiggle because they are absorbing energy. The energy left over (the
energy that doesn’t get absorbed) can be turned into something called an IR spectrum.
The dangling peaks on an IR spectrum appear in places that are unique for each kind
of bond.
carbonyl
C-H bonds
(~3000)
C=O
(1700±50)
C-H bonds
(~3000)
C=O fingerprint region

(1700±50) (ignore)
wavenumbers (ν), units are cm-1 or 1/cm
higher wavenumber ≈ higher-energy bond movement

Peaks You Should Memorize!
If you see the following on your IR spectrum: Then your compound has a:
Small to medium peak at 1600–1700 cm-1 C=C or C=N
A BIG pointy peak at 1700 ± 50 cm-1 C=O (carbonyl)
A LARGE, broad trough far to the left for alcohols and

OH
on top of 3000 cm-1 for carboxylic acids
C-H’s
Big, pointy peaks coming straight down around 3000
(sp’s are to the left of sp2’s,
cm-1
which are to the left of sp3’s)
N-H
A sharp peak to the left of 3000 (around 3200-3500)
(one peak for –NH, two peaks for –NH2)
Medium-sized peak at ~2200 CºN (a nitrile)
Vampire teeth at 1500-1600 and 1300-1400 NO2


OH
C-H’s
cm-1
N-H


OH
C-H’s
cm-1
N-H


Because IR spectroscopy tells you what kinds of bonds are found in your
OH
molecule, IRof spectroscopy
on top is used
3000 cm-1 for carboxylic acids most often to determine molecule’s
functional groups. C-H’s
cm-1
N-H

The C=O (Carbonyl)
carbonyl
C-H bonds
(~3000)
C=O
(1700±50)
The OH Stretch (Alcohols)

OH
OH
OH
(far left)
The OH Stretch (C. Acids)

OH
carboxylic
acid
wide
Where’s the OH?
the OH!
C=O
(1700±50)
C-H bonds
(~3000)
The OH Stretch (C. Acids)
Alcohol OH’s appear to the left of 3000, around 3400 to 3600. Carboxylic
acid OH’s shift slightly to the right, which places them on
OH top of your CH
peaks at ~3000. This makes your CH peaks wider at the top, because
carboxylic
there’s an OH trough buried beneath them. acid
wide
InWhere’s the OH?
other words, if you have a C=O (carbonyl) at 1700±50 AND a widening
of your CH peaks at ~3000, then you probably have a carboxylic acid.
Carboxylic acids are also super easy to spot using 1H-NMR spectra, which
we’ll talk abouttheinOH!
a later video.
C=O
(1700±50)
C-H bonds
(~3000)
Some Examples
What kind of peaks would you expect to see in an IR spectrum of the following
compound?
C=O
OH
C=O
OH (1700±50)
C-H bonds
Some Example
carboxylic
acid
wide
the OH!
C=O
(1700±50)
C-H bonds
(~3000)
The CºN Stretch
Cº N
Cº N
(~2200)
The NO2 Stretch
NO2
NO2 (~1600 and ~1400)

Amines and Amides
N-H
Amines and Amides
N-H
NH2
CH’s
NH2
not a C=O
Amines and Amides
N-H
CH’s
(~3000)
amide
NH2 C=O
(1700±50)
Amines and Amides
N-H
CH’s
NH
not a C=O
Amines and Amides
N-H
amide
CH’s
(~3000)
NH C=O
(1700±50)
Amines and Amides
N-H
Amines give off sharp amine peaks to the left of your CH peaks at ~3000,
but do NOT give C=O (carbonyl) peaks at 1700±50. Amides giveamide both
amine peaks and carbonyl peaks.
CH’s
(~3000)
NH C=O
(1700±50)
UV-Vis Spectroscopy
UV-Vis spectroscopy is another technique you can use to help identify a
compound’s structure. Basically, you throw a compound into a UV/Vis spectrometer,
where it’s bombarded in sequence by UV and visible light. The compound absorbs
some of that light and then transmits the rest. The light that gets transmitted is
collected to produce a spectrum. The only thing you need to know about this
technique is that UV-Vis spectroscopy is used mostly to analyze compounds with
conjugated double bonds:
UV-Vis Spectroscopy
UV-Vis spectroscopy is another technique you can use to help identify a
compound’s structure. Basically, you throw a compound into a UV/Vis spectrometer,
where it’s bombarded in sequence by UV and visible light. The compound absorbs
some of that light and then transmits the rest. The light that gets transmitted is
collected to produce a spectrum. The only thing you need to know about this
technique is that UV-Vis spectroscopy is used mostly to analyze compounds with
conjugated double bonds.
H2
H2C C CH2 H
H2C C CH2 C H2C C
C
H H C CH2
acumulated
cumulated H
diene
double bonds anisolated
isolated
double bonds
diene a conjugated anotherbonds
conjugated double conjugated
diene diene
Mass Spectrometry
Mass spectrometry is a technique that lets you determine a compound’s mass. For
example, if your compound has a molecular formula of C3H6O, then its mass is
approximately:
(12 x 3) + (1 x 6) + 16 = 58
So if you ran a sample of this compound in a mass spectrometer, the machine would
tell you that your compound’s mass is 58.
Mass Spectrometry
your sample
electrons detector
goes in here
spray your
sample
computer
Mass Spectrometry
1- 1- 1-
- -
CH3 e CH3 e
H3C
+ CH2
[C8H10]
e
- [C6H5] [C2H6]
MW = 106.165
MW = 77.104 MW = 29.061
1- 1-
CH2
molecular ion (M)
(“parent peak”) + CH3
[C7H7] [CH3]
MW = 91.130 MW = 15.035
We would likely see peaks for all of these ions, as well as many more. The most
stable ion in the entire mix produces the tallest peak, called the base peak.
Remember, though: the tallest peak does not necessarily correspond to the
molecule’s molecular mass peak, also called the “M” peak, molecular ion peak, or
the parent peak.
Mass Spectrometry
1- 1- 1-
- -
CH3 e CH3 e
H3C
+ CH2
[C8H10]
e
- [C6H5] [C2H6]
MW = 106.165
MW = 77.104 MW = 29.061
1- 1-
CH2
molecular ion (M)
(“parent peak”) + CH3
[C7H7] [CH3]
MW = 91.130 MW = 15.035
The base peak (the tallest peak) only tells you which of all the fragments produced is
the most stable and hence, the most abundant. The abundances of all the other
peaks are calculated relative to the base peak. Also, peaks are separated by their
mass-to-charge ratio, or m/z.
Mass Spectrometry
91.130
(base peak)
106.165
(parent peak)
Degrees of Unsaturation
When identifying compounds’ structures, sometimes it’s helpful to extract
information about their formulas.
Alkanes have the general formula CnH2n+2. Alkenes have the general formula
CnH2n. Alkynes have the general formula CnH2n–2. As you can see, each time we
add a double bond, it decreases the number of hydrogens by two. The same thing is
true if we add a ring, as in a cycloalkane.
H H H
C
H C H H C C H
C
H H H
An alkyne
CnH2n–2
An alkane An alkene a cycloalkane
CnH2n+2 CnH2n CnH2n
Each added double bond or ring is called a degree of unsaturation. Each
degree of unsaturation decreases the number of hydrogens by 2. Thus, we
could say that the number of degrees of unsaturation equals:
# of degrees of unsaturation = # of double bonds or rings = (A – B)/2
Where A is the number of hydrogen atoms your compound would have if it didn’t
have any double bonds or rings (CnH2n+2), and B is the number of hydrogen
atoms your compound in question actually has.
Here’s how I determine the number of degrees of unsaturation:
• Count how many carbons I have in my given formula.

• Draw a molecule that has that same number of carbons, but NO double bonds
or rings. If there are non-hydrogen atoms in my formula, I put them into the
structure I draw. I then add H’s to the structure, wherever needed.
• Figure out what the formula is for the structure I just drew. If it matches the one
I’ve been given, then the formula I’ve been given has ZERO degrees of
unsaturation.
• If it doesn’t, then I add a double bond and repeat Step 3. If my formula matches
now, then it has ONE degree of unsaturation.
• If it doesn’t, then I add another double bond and repeat Steps 3-4. If my formula
matches now, then it has TWO degrees of unsaturation.
• Repeat this process until I get a matching formula.
Example
How many degrees of unsaturation does the following formula have: C3H6O?
H H H H H
H C C C OH H C C C O
H H H H H H
C3H8O C3H6O
one degree of
unsaturation
13C-NMR Spectroscopy
A typical 13C-NMR spectrum looks like this:
2 3 4
The labeled peaks are each

produced by a different kind
of carbon atom. By learning
where different kinds of
carbons show up on a 13C-
1 NMR spectrum, we can
deduce compounds’
structures.
What do I mean by “different kinds” of carbons?
If two different carbon atoms are in exactly the same environment –that is, they have
the EXACT same stuff all around them in all directions– then they are the “same kind
of” (or “equivalent”) carbons. The number of peaks (signals) we see on our 13C-
NMR spectrum will equal the number of non-equivalent (different) carbon atoms in
our molecule. How many different kinds of carbon atoms are there in the following
molecules?
Where do different peaks show up?
The more positively-charged an individual carbon is, the further to the left it will
appear on an 13C spectrum. The more negatively-charged, the further to the right it
will appear.
Further left = more downfield = more “de-shielded”

= more positively charged
Further right = more upfield = more “shielded”

= more negatively charged
Most organic textbooks give long lists of where different kinds of carbons show up on
a 13C-NMR. I personally think those lists are usually way longer and more complicated
than necessary. Here’s my list:
Kind of carbon: Where it shows up:
Alkane carbons 0-70 ppm
Alkene carbons 90-120 ppm
Aromatic carbons (like C’s in benzene rings) 110-160 ppm
Carbonyl (C=O) carbons
• Esters, amides, and carboxylic acids 160-180 ppm
• Aldehydes and ketones >200 ppm
TMS (tetramethylsilane) – not part of your
0 ppm
compound!
O O O
C C C
OH NH2 OR
carboxylic acids amides esters
220 200 180 160 140 120 100 80 60 40 20 0
O O
C C
H R R
aldehydes ketone
1H-NMR Spectroscopy
A typical 1H-NMR spectrum looks like this:
The labeled peaks are each

produced by a different kind
1 of hydrogen atom. By
learning where different
kinds of hydrogen atoms
show up on a 1H-NMR
spectrum, we can deduce
compounds’ structures.
What do I mean by “different kinds” of hydrogens?
Just as with 13C-NMR, if two different hydrogens are in exactly the same environment
–that is, they have the EXACT same stuff all around them in all directions– then they
are the “same kind of” (or “equivalent”) hydrogens. The number of peaks (signals)
we see on our 1H-NMR spectrum will equal the number of non-equivalent (different)
hydrogen atoms in our molecule. How many different kinds of hydrogen atoms are
there in the following molecules?
As with 13C-NMR, the more positively-charged an individual hydrogen is, the further to
the left it will appear on a 1H spectrum. The more negatively-charged, the further to
the right it will appear.
Further left = more downfield = more “de-shielded”

= more positively charged
Further right = more upfield = more “shielded”

= more negatively charged
Most textbooks give long lists of where different kinds of hydrogens show up on a 1H-NMR. I personally
think those lists are usually way longer and more complicated than necessary. Here’s my list:
Kind of hydrogen: Where it shows up:
H’s stuck to sp3-hybridized carbon atoms 1-5 ppm, depending on what other
(single-bonded CH3’s, CH2’s, and CH’s) atoms are nearby
H’s stuck to a C=C carbon 4-6 ppm
H’s stuck to aromatic rings like benzene 6-8 ppm
Aldehyde H’s ~10 ppm

Phenol H’s (sometimes) ~10 ppm
Carboxylic acid H’s 12-14 ppm
Amide H’s (sometimes) 11-13 ppm
Alcoholic OH’s 0.5 – 5.5 ppm
Amine NH’s 0.5 – 5.5 ppm
TMS (tetramethylsilane) – not part of your compound! 0 ppm
R H
N
R O H
H
O
OH alcohols amines
H 0.5 - 5.5 ppm
phenols aldehydes
double-bond land
(H’s stuck to C=C)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
aromatic land single-bond land

(H’s stuck to (H’s stuck to sp3-hybridized TMS (not part of
O
O benzene) C’s) your compound!)
H
N
O H
H
carboxylic acids amides
Integrals
On some 1H-NMR spectra, we see numbers written above the peaks, like these:
9 These numbers are called

integrals. What do they mean?
Well, how many A hydrogens

3
does our compound have? How
many B hydrogens does it have?
Integrals
On some 1H-NMR spectra, we see numbers written above the peaks, like these:
peak for B 9
hydrogens A hydrogens: 3
B hydrogens: 9
3
So these integral numbers tell you
how many H’s there are in each
signal.
peak for A
hydrogens
Splitting
One last thing about 1H-NMR (which doesn’t apply to 13C-NMR): hydrogen atoms
“split” the signal of neighboring hydrogen atoms. For example:
A B
H3C CH2Br
In this molecule, hydrogens A are next-door to hydrogens B. Thus, hydrogens B will

“split” hydrogens A, and hydrogens A will “split” hydrogens B. This means that their
individual peaks won’t be simple vertical lines, but will be a triplet and a quartet.
(Note: OH’s and NH’s often don’t split or experience splitting.)
Splitting
A B
H3C CH2Br
So how do hydrogens A “split” the peak for hydrogens B, and vice versa?
Remember the “n+1” rule:
Hydrogens A look next-door and see two hydrogens B (n=2). The signal for
hydrogens A gets “split,” then, as follows:
n + 1:
2+1=3
So the signal for hydrogens A will be a triplet.
Similarly, hydrogens B look next-door and see three hydrogens A (n=3). The signal
for hydrogens B, then, will be:
3 + 1 = 4: a quartet.
3
A few relevant details
A B
H3C CH2Br • Hydrogens B appear further
Hydrogens A to the left (further downfield)
(a triplet) than hydrogens A because
2 hydrogens B are more
positively-charged (because
they’re closer to the
bromine).
Hydrogens B TMS (not part of
(a quartet) your compound!) • Hydrogens A integrate for
3, and hydrogens B for 2,
because there are three A
hydrogens and two B
hydrogens.
To Recap
• Each “different kind of” (or “non-equivalent”) hydrogen gives a different signal. The
more positively-charged, the further to the left (downfield).
• The integral numbers above each peak tell you how many hydrogens are in that
peak.
• Hydrogens get split by neighboring hydrogens. To figure out the splitting, count all
the hydrogens next-door in all directions and add 1 (n+1 rule)
• Remember the following:
Alcohol & amine H’s
Phenol and double-bond land (0.5 - 5.5 ppm)
aldehyde H’s (H’s stuck to sp2-
hybridized C’s)
14 13 12 11 10 9 8 7 6 5 4 3 2 1 0
aromatic land single-bond land TMS (not part of

Carboxylic acid & (H’s stuck to (H’s stuck to sp3-hybridized your compound!)
amide H’s benzene) C’s)
Textbook Versus Reality
Br Br
A
A B
H3C H
6 5 4 3 2 1 0
PPM
textbook spectrum
real spectrum
C
H2
A O C
H3C C Br
H2
A B
C B
4 3 2 1 0
PPM
textbook spectrum
real spectrum
A A
A H2 H2
C C
Cl C Cl
H2
B
B
4 3 2 1 0
PPM
textbook spectrum
real spectrum
O
C A
A B H2
H3C C C D
H
C O CH3
D
CH3 A
C
B
5 4 3 2 1 0
PPM
textbook spectrum
real spectrum

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Spectroscopy

Infrared (IR) Spectroscopy

bond stretching bond bending

C=O fingerprint region

wavenumbers (ν), units are cm-1 or 1/cm

higher wavenumber ≈ higher-energy bond movement

Small to medium peak at 1600–1700 cm-1 C=C or C=N

A BIG pointy peak at 1700 ± 50 cm-1 C=O (carbonyl)

A LARGE, broad trough far to the left for alcohols and

Vampire teeth at 1500-1600 and 1300-1400 NO2

Small to medium peak at 1600–1700 cm-1 C=C or C=N

A BIG pointy peak at 1700 ± 50 cm-1 C=O (carbonyl)

A LARGE, broad trough far to the left for alcohols and

Vampire teeth at 1500-1600 and 1300-1400 NO2

Small to medium peak at 1600–1700 cm-1 C=C or C=N

A BIG pointy peak at 1700 ± 50 cm-1 C=O (carbonyl)

A LARGE, broad trough far to the left for alcohols and

Vampire teeth at 1500-1600 and 1300-1400 NO2

Small to medium peak at 1600–1700 cm-1 C=C or C=N

A BIG pointy peak at 1700 ± 50 cm-1 C=O (carbonyl)

Vampire teeth at 1500-1600 and 1300-1400 NO2

A LARGE, broad trough far to the left for alcohols and

A LARGE, broad trough far to the left for alcohols and

Medium-sized peak at ~2200 CºN (a nitrile)

Vampire teeth at 1500-1600 and 1300-1400 NO2

NO2 (~1600 and ~1400)

# of degrees of unsaturation = # of double bonds or rings = (A – B)/2

• Count how many carbons I have in my given formula.

The labeled peaks are each

Further left = more downfield = more “de-shielded”

Further right = more upfield = more “shielded”

220 200 180 160 140 120 100 80 60 40 20 0

The labeled peaks are each

Further left = more downfield = more “de-shielded”

Further right = more upfield = more “shielded”

H’s stuck to a C=C carbon 4-6 ppm

H’s stuck to aromatic rings like benzene 6-8 ppm

Aldehyde H’s ~10 ppm

aromatic land single-bond land

9 These numbers are called

Well, how many A hydrogens

In this molecule, hydrogens A are next-door to hydrogens B. Thus, hydrogens B will

So the signal for hydrogens A will be a triplet.

aromatic land single-bond land TMS (not part of

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