1. Qualitative Organic Chemistry
The science of identifying unknown organic compounds

2. Qualitative organic chemistry
You arrive at work to find a bottle of an unknown chemical on your desk with a note attached – “what is this?”
You have no access to the IR, NMR, MS or UV/VIS
Can you determine anything about this compound? How?
Qualitative organic chemistry

3. Physical appearance You can note the physical appearance of the sample
Solid, liquid?
Crystalline form, colour
Odour
Viscosity
Density
Etc.
Physical appearance

4. Physical appearance

5. Simple physical tests If it is a solid, you can obtain a mp
A bp can be obtained for a liquid
Does a mp tell you very much about the compound? Are all mp’s unique?
(there are about 16 million known organic compounds out there)
Simple physical tests

6. The mp may help you determine something about the compound
Is it a very low or very high mp (small mw compound, an organic salt?)
If you have any suspicions about the compound you can check the mp to see if you are on the right track
Simple physical tests

7. A classic old way of confirming the ID of a compound – the mixed melting point
Mix the unknown with a pure known sample
Take the mp
If the mp stays the same as the pure compound, you have a good chance of being correct
(if you add two dissimilar compounds together, the mp will decrease)
Mixed mp

8. solubility You can check to see what the sample dissolves in
If it is water soluble it is polar
It is also likely to be a low mw compound
solubility

9. If it does not dissolve in water (most organics do not), then see if it will dissolve in dilute acid or base
If it dissolves in an acid, it is basic (in organic chemistry, this usually means it is an amine)
If it dissolves in a base, it is acidic (a carboxylic acid, a phenol, or a sulfonic acid)
Solubility

10. If it dissolves in both sodium bicarbonate and sodium hydroxide it is probably a carboxylic acid
If it dissolves in sodium hydroxide but not in sodium bicarbonate it is probably a phenol
solubility

11. Solubility flow chart

12. There is a selection of other solvents which may be tried to narrow down the possibilities
However, to pin down the absolute identity of a compound on solubility alone is a pretty remote concept
solubility

14. Molecular weight of an acid by titration
If you suspect based on solubility tests that you have a carboxylic acid, you can determine its molecular weight by titrating with standard base
If know the grams of acid in your sample and the # moles it represents from the titration:
Moles = g/mol wt
Molecular weight of an acid by titration

15. If you are a typical organic chemist, you could burn it in the flame of a bunsen burner
If it burns with a sooty black flame, it probably contains a benzene ring
No sooty flame – no benzene ring
Clear blue flame – probably an unsaturated compound (or highly oxygenated compound)
What else can we do?

16. Dip a copper wire into a solution of the compound and then burn it in a flame
The Beilstein test – a green flame indicates a halogenated compound
More flame tests

17. Add sample to a test tube complete with a small lump of sodium metal
Heat (and take cover)
Reaction with hot sodium leads to decomposition of the sample
Can now analyze for various elements
Eg chloride determined by adding silver nitrate
The Sodium Fusion test

18. Functional group tests
There are a large number of chemical spot tests that may be used to further narrow down the possibilities
Different functional groups react with certain reagents to produce characteristic colours or precipitates (or the release of a gas)
Functional group tests

19. React with a solution of ferric chloride to produce a purple colour
phenols

20. React with a reagent (2,4- dinitrophenylhydrazine or 2,4-DNP) to form a yellow to orange precipitate
Aldehydes react with another reagent (Tollen’s reagent) to form a silver mirror surface on a test tube
Methyl ketones react with another reagent (iodoform test) to produce a pale yellow precipitate
Aldehydes and ketones

21. Spot tests

22. React with chromate oxidizing agents – change colour from red to green (Jones’ reagent)
React with acetyl chloride to produce heat
Can tell whether the alcohol is primary, secondary or tertiary using Lucas reagent (Zn/HCl) and gauging the speed and ease of reaction
alcohols

23. And so on and so on …

24. So what info do we have so far?
By now, we should know the functional group(s) the compound contains
We still do not know the exact compound we have in the bottle however
So what info do we have so far?

25. In the classical tradition, at this point we would do one of two things
We would consult an extensive set of tables to match our mp with known precisely determined mp’s and make an educated guess
Then check all of the available physical data against our own (appearance, solubility, etc, etc)
Where next?

26. OR… We could create a derivative of our sample and purify it
We then would take the mp and check it against a derivative table
If both the mp of our original compound and that of our derivative were the same, there was a very good chance we had identified our sample correctly
OR…

27. Derivatization

28. We could also determine an approximate mw of our compound by:
Boiling point elevation
Freezing point depression
Titration (works very well for carboxylic acids)
Molecular weight

29. Freezing point depression
The change in the freezing point is related to the concentration (in molality) of the compound
Using equations, you can easily calculate the mw based on the freezing point change and the quantity (in grams) of the unknown used

30. Time and labour
So why do we no longer pursue the classical organic procedures to their ultimate conclusion?