3.

For A Hydrocarbon With No Rings Or

Double Bonds The Number Of Hydrogens Is
Equal To Twice The Number Of Carbons, Plus
2
You should be able to see that for a hydrocarbon with no rings or double bonds, the number of
hydrogens is equal to twice the number of carbons, plus 2.

So for a molecule like dodecane (C12) we’d expect to see (12 x 2) + 2 = 26 hydrogens.

Now: what happens to the molecular formula when we add a double bond to the molecule?

4. Each Double Bond or Ring Reduces The

Hydrogen Count By 2
You should be able to see that each multiple bond (π bond ) the number of hydrogens in the
formula decreases by two. Ethyne (2 π bonds) has two fewer hydrogens than ethene (1 π bond),
which has two fewer hydrogens than ethane (zero π bonds).

Hydrocarbons containing  π bonds are often called “unsaturated” hydrocarbons. They can be
treated with hydrogen (Pd/C, H2 ) to give the corresponding alkane with no  π bonds, which is then
said to be “saturated” with hydrogen. (Compare “unsaturated fats“, which contain alkenes, and
“saturated fats” which do not).

Since every pi bond results in a loss of 2 hydrogens from the molecular formula, we refer to this
to as a “degree of unsaturation“.

Let’s turn our attention to cyclic compounds. Do you notice a similar effect?
You should! Every ring in the molecule decreases the number of hydrogens by two.

5. Each Ring Or Double Bond Is Called A

“Degree Of Unsaturation”
Therefore, each ring introduces a “degree of unsaturation” into the molecule. 

You might ask: what if we have a molecule with rings and multiple bonds? See for yourself.
The effect is additive. That is, the “degrees of unsaturation” is the sum of the number of double
bonds and rings.

Note that it doesn’t tell you how many double bonds are present or how many rings are present.
It merely tells you their sum.

6. Example: Benzene (4 Degrees Of

Unsaturation)
For instance, thus the molecular formula C6H6 (4 degrees of unsaturation) is satisfied by
molecules with

 4 pi bonds
 3 pi bonds and a ring (benzene)
 two pi bonds and two rings (the very unstable Dewar Benzene, synthesized in 1963)
 one pi bond and three rings (the even more unstable benzvalene, a contact explosive,
synthesized in 1971)
 and yes, even zero pi bonds and four rings (prismane, synthesized in 1973).
[Historical side note: the formula of benzene was known to be C6H6 from Michael Faraday in
1825, but the correct structure was not proposed until 1865 (Kekule) and not confirmed until
1929, by Catherine Lonsdale’s X-ray studies [h/t BRSM]. Just a reminder that knowing
the molecular formula only gets you so far. ]

Helpful hint: if you see 4 degrees of unsaturation in an unknown molecule, thinking “benzene
ring” is a good place to start.

7. What About Molecules Containing Oxygen?

So far, so good.  Let’s move on. What about molecules with oxygen?

The same rules apply! We can calculate the number of hydrogens from the number of carbons as
if the oxygen didn’t exist.

Note that a π bond which contains oxygen still counts as a “degree of unsaturation” (see
formaldehyde, CH2O).
8. What About Halogens?
OK. What about halogens like chlorine, fluorine, iodine and bromine?

For the purposes of our formula relating hydrogens to carbons for molecules without rings or
double bonds, halogens can be counted as hydrogens. That is, carbon tetrachloride (CCl4) has
the same degrees of unsaturation (zero) as CH4.

We can thus modify the equation for a molecule with no double bonds or rings as follows:

9. Nitrogen Is A Little Bit Tricky

We’ve saved nitrogen for last, because it’s a bit weird.  Try to see the pattern of how nitrogen
affects our formula.
OK, you might have noticed that we can’t ignore nitrogen like we did oxygen.

The way to make the equation work with nitrogen is to add the nitrogen count to the right hand
side of the equation, like this:

Try it with cadaverine (C5H14N2) which contains no double bonds or rings.

10. A Unified Formula For Degrees of

Unsaturation
So far our equation has only applied to “saturated” compounds with no double bonds or rings.

How can we use this to make a general formula for “degrees of unsaturation”, which is
actually… useful?

Math time. If we move the left hand side over to the right, we get this:
Zero equals the degrees of unsaturation in this case.

If we introduce a double bond or ring, the equation will return “2”.

Each successive degree of unsaturation will increase this number by 2. For instance, 2-
chloropyridine C5H4NCl gives us 8:

Now 8 is not the degrees of unsaturation. It’s merely the number of hydrogens “missing” from
the corresponding non-cyclic alkane of the same carbon count.

In order to make this equation give us the actual degrees of unsaturation, we need to divide
everything by two.

We can really condense things by using the symbols H, C, N, and X to represent hydrogens,
carbons, nitrogens and halogens, respectively.
This is our final form for the equation for “degrees of unsaturation”, or “index of hydrogen
deficiency” if you prefer.

11. Applying The IHD Formula To Four Real-

Life Examples
OK, now for those real-life examples I mentioned above.

 C9H8O4     
 C21H30O2 
 C17H21NO4 
 C11H15NO2 
Let’s plug each of them into our formula. You should get:

 C9H8O4     [6 degrees of unsaturation]

 C21H30O2 [7 degrees of unsaturation]
 C17H21NO4 [8 degrees of unsaturation]
 C11H15NO2 [5 degrees of unsaturation]
Now, let’s look at each of the molecules. You’ll find that the calculated degrees of unsaturation
agrees with the sum of [multiple bonds and rings] in the molecule.
Super useful. Super easy.

With the structure in front of you it seems obvious. But if you’re dealing with an unknown it can
be very helpful, like we saw with deer tarsal gland hormone in the last post.

In the next post, we’ll start delving into the mysteries of spectroscopy. We’ll start with one of the
simplest spectroscopic techniques – UV-Vis spectroscopy – and show how it can be used to
deliver clues about the structures of various molecules.