Reminder: These notes are meant to supplement, not replace, the textbook and laboratory manual.

Qualitative Organic Analysis 2

1. You are required to recognize functional groups when you see them, and give examples of
members of functional group families. Here are the functional groups, with examples.
First, the hydrocarbons (compounds containing only carbon and hydrogen):
H methane
|
RH, alkanes H—C—H
| cyclopentane
H benzene, an
aromatic
RCH=CH 2 , alkenes CH2 =CH 2 , ethylene hydrocarbon
RC≡CH, alkynes HC≡CH, acetylene

Many organic compounds that contain halogens can be classified as 1˚, 2˚, and 3˚. To
decide whether a halide is primary, secondary, or tertiary, count the number of carbon atoms
attached to the carbon that has the halogen bonded to it. Therefore, general formulas for
primary alkyl halides can be written as RCH2 X, secondary ones as R2 CHX, and tertiary
ones as R3 CX. If the halogen is bonded to an sp2 carbon, the compound is not classified
this way, but rather as a vinyl or aryl halide.
F
Br 1-bromobutane, 1˚
fluorobenzene
I iodocyclopentane, 2˚
ClCH=CH 2 , vinyl chloride
CH3
|
CH3 —C—Cl tert-butyl chloride, a 3˚ alkyl halide (IUPAC
| name 2-chloro-2-methylpropane)
CH3

Compounds containing a single oxygen atom include alcohols (ROH), ethers (ROR'),
phenols (ArOH), aldehydes (RCHO), and ketones (RCOR'). Alcohols are further classified
as 1˚, 2˚, and 3˚, in the same way that alkyl halides are.
O
OH ethanol, 1˚ || acetaldehyde, an aldehyde
CH3 C-H
2-propanol, 2˚ O
OH || acetone, a ketone

tert-butyl alcohol, a 3˚alcohol OH

OH (IUPAC: 2-methyl-2-propanol)
phenol
CH3 CH2 OCH 2 CH3 , ethyl ether
 Here are carboxylic acids (RCO2 H or RCOOH) and their derivatives, including acid
chlorides (RCOCl), anhydrides, esters (RCO2 R"), and amides (RCONH2 etc.).

O O ethyl acetate, an ester

|| acetic acid, a carboxylic acid ||
CH3 C-OH CH3 C-O-CH 2 CH3

O O
acetyl chloride, an acid
|| || acetamide, an amide
CH3 C-Cl chloride (or acyl halide) CH3 C-NH 2
O
O O ||
| | | | acetic anhydride, an anhydride NH
CH3 C-O-CCH 3 this is also an amide

Amines are classified as 1˚, 2˚, and 3˚, but not they way alcohols and alkyl halides are. A
primary amine is RNH2 , a secondary amine is R2 NH, and a tertiary amine is R3 N. You
count the number of atoms attached directly to the N to classify amines.

NH 2 ethanamine, 1˚ NH 2
aniline, a 1˚
aromatic amine
NH 2 2-propanamine, 1˚

tert-butyl amine, a 1˚amine N—CH 3 a 3˚ amine

NH 2
CH3 CH2 NHCH 2 CH3 , diethylamine, secondary

2. Common organic compounds used in CHEM 2230L and 2240L include these. First, here
are some hydrocarbons and an alkyl halide.
CH3 CH3 CH3
this is p-xylene,
one of three
xylene isomers
CH3 methylcyclohexane toluene

H
|
cyclohexane cyclohexene Cl—C—Cl
naphthalene |
H
pentane is the main component dichloromethane
of petroleum ether
 Next, here are some compounds containing one oxygen atom: alcohols, ethers, aldehydes,
and ketones.
OH O O O
| || || ||
C-H C

cyclohexanol cyclohexanone benzaldehyde

benzophenone
(CH3 )3 COCH 3
CH3 CH2 OH MTBE O
ethanol methyl tert-butyl ether acetone ||
CH3 CCH3

These are carboxylic acids and esters. (Aspirin is both.)

CO2 H O O
O CO2 H
|| ||
OH ||
C-OH O—C—CH 3
CH3 COH
acetic ethyl acetate
aspirin
salicylic acid O
acid ||
benzoic CH3 C-OCH 2 CH3
acid

These compounds include two anhydrides, an amide, and urea.

O O
|| || acetic O O
NH-C-CH3 H2 N-C-NH2 anhydride || ||
CH3 —C—O—C—CH 3
urea

maleic O
O O
acetanilide anhydride

3. To predict the results of solubility tests of known compounds, and to use solubility test
data to classify unknown compounds, you must know what the solubility tests do. Some of
these tests are useful as stand-alone tests, but to get the best possible information, follow the
whole scheme. For the purposes of these tests, “soluble” means “one drop of unknown
will dissolve in one mL of solvent”.

Solubility in water
If a compound is soluble in water, it is a compound of about four carbons or less
that contains N or O (or it may contain more than one functional group). The solution is
then tested with litmus paper.
If the solution turns blue litmus red, the unknown is a carboxylic acid (RCO2 H).
If the solution turns red litmus blue, the unknown is a basic compound, an amine
(RNH 2 , R2 NH, or R3 N).
If the solution is neutral to litmus, the unknown includes a neutral O- or N-
containing functional group such as alcohol, ether, aldehyde, ketone, ester, or amide.
If the compound is insoluble in water, go on to the next solubility test.

Solubility in 5% NaOH
If the compound is soluble in this solution but insoluble in water, it is acidic, either a
phenol (ArOH) or a carboxylic acid (RCO2 H). This is reaction solubility, not like-
dissolves-like solubility; the alkaline test solution reacts with acidic compounds to give
water-soluble products. Sample equations are:

OH + OH -----> H2 O + O

COOH + OH -----> H2 O + COO

You must run the water solubility test first for this test to be useful; 5% NaOH is 95%
water, and compounds that dissolve in water also dissolve in 5% NaOH because of that.
To distinguish between phenols and carboxylic acids, you can use the NaHCO3
solubility test (next).
If the compound is insoluble in 5% NaOH, go to the 5% HCl solubility test.

Solubility in 5% NaHCO3
Sodium bicarbonate is weaker as a base than NaOH. NaHCO3 is an ingredient of
some over-the-counter medications that react with excess stomach acid, but NaOH is far too
strong a base, and therefore far too dangerous, for that. This is another reaction-solubility
test; bicarbonate ion reacts with carboxylic acids but not with phenols to produce water-
soluble salts. The reaction also gives carbon dioxide, and these bubbles are visible, making
this a useful stand-alone test for carboxylic acids. You will use it that way in the lab.

COOH + HCO3 -----> H2 O + CO2 + COO

OH + HCO3 -----> no reaction

Solubility in 5% HCl
This is yet another reaction-solubility test. Basic organic compounds (amines) react
with the acid to give water-soluble products. As with the 5% NaOH test, it is necessary to
test with water first, for the same reason. A sample equation is:

NH 2 + H3O -----> H2 O + NH 3

If the compound is insoluble in 5% HCl, go to the next (and last) solubility test.

Solubility in concentrated H2 SO4

Alkenes, alkynes, and compounds that contain N and O are protonated by this
extremely powerful acid, and the products of these reactions dissolve. Concentrated sulfuric
acid is approximately 94% acid. Compounds that contain only alkyl groups, halogen atoms,
and benzene rings (RH, RX, ArH, ArX) will fail to dissolve.
4. Simple chemical tests are fast reactions that give results that are immediately visible.
They generally take advantage of functional group chemistry. Modern chemists more often
use infrared spectroscopy to identify functional groups, but these tests still have their place.
This is not a scheme, the way the solubility test scheme is; the tests can be performed in
almost any order.

Bromine in carbon tetrachloride

This test is positive for alkenes and alkynes. These compounds cause the test
solution to decolorize (that is, the red-brown color of Br2 to disappear) almost instantly.
The organic reactant and products are almost always colorless. A sample equation is:

CCl4 Br
plus its
+ Br2 ------->
Br enantiomer

Cold alkaline potassium permanganate

This test is positive for alkenes and alkynes. These compounds cause a brown
precipitate of MnO2 to form almost instantly from the purple permanganate solution.

OH , cold OH
+ MnO4 ---------------> MnO2 +
OH

2,4-Dinitrophenylhydrazine (DNP) test

This test is positive for both aldehydes and ketones. A positive test is a yellow,
orange, or red precipitate, a 2,4-dinitrophenylhydrazone, that forms from the red DNP
reagent solution. Small crystals and unconjugated aldehydes or ketones give precipitates
toward the yellow end of the scale; large crystals made from conjugated compounds tend to
be more red. A sample equation is:
O2 N

NO 2
O N-NH NO 2
|| ||
CH3 CCH3 + O2 N NHNH2 -------> CH3 CCH3

+ H2O

Tollens’ test
This test is positive for aldehydes only. A positive Tollens' test is the formation of a
silver mirror on the inside of the reaction container. If the container is dirty, you’ll often get
a black precipitate instead of a mirror. A sample equation (not balanced) is:

RCHO + Ag(NH3 )2 + -----> RCO2 – + Ag 0

Note: Silver ammonia complex, the Tollens’ reagent, also gives a white precipitate with
terminal alkynes. The equation for that is:

Ag(NH3 )2 +
RC≡CH ----------------> RC≡CAg (s)
 Jones (chromic acid) test.
This test is positive for 1˚ and 2˚ alcohols and aldehydes. A positive test is a green
suspension of Cr3+ that forms from the red chromic acid solution. Sample equations are:

RCH2 OH + H2 CrO4 -----> RCOOH + Cr3+

RCHO + H2 CrO4 -----> RCOOH + Cr3+
RCHOHR’ + H2 CrO4 -----> RCOR’ + Cr3+

Ferric chloride test.

This test is positive for phenols. A positive test is the formation of a purple solution
from the pale rusty-orange FeCl3 test reagent.

5. Safety considerations for this experiment include:

Handle all test reagents with care. Some of them are relatively harmless (water for
the solubility test, sodium bicarbonate solution, ferric chloride test reagent), but you don't
want to develop bad habits in the laboratory.
Of the test reagents you will be using, the Jones reagent and the DNP reagent are
both corrosive (acidic) and toxic. Be especially careful with these.
Tollens' reagent is also somewhat corrosive (alkaline) and toxic, and forms
compounds on standing that may explode spontaneously. This is why you are directed to
pour your completed Tollens' test materials into the beaker of nitric acid in the hood; acid
destroys the potential for these explosions. Your instructor will destroy all unused Tollens'
reagent at the end of the day.
Of the test reagents described above that you will not be using in this lab, 5%
NaOH, 5% HCl, concentrated sulfuric acid, bromine in carbon tetrachloride, and potassium
permanganate are all corrosive and toxic.
All of the knowns and unknowns in this experiment are at least mildly toxic and
flammable. Use the usual precautions in handling them.

Notes for topics that may be included in quizzes given during the second week of qualitative
analysis experiments:

6. You may be asked to predict the product of reactions that take place during positive
solubility tests and simple chemical tests. These include the NaOH, NaHCO3 , and HCl
solubility tests, and the bromine in carbon tetrachloride, cold permanganate, Tollens', Jones
(chromic acid), and DNP tests. Sample equations are included in the information about
these tests given in sections 3 and 4 above.