Separation and Purification of Organic Compounds

 Numerous purification methods are available to the organic chemist.

 Each technique has advantages and disadvantages depending on the reagents involved and the desired results.

Techniques Known as Basis Principle Process Additional Info

Solution and Solid-liquid Relative solubility - employing a solvent 1. Sugar and
Filtration extraction of components wherein some benzoic acid
components are soluble 2. Dissolve in H2O
Separation: while others are not 3. Sugar dissolves
insoluble - One of the while benzoic acid
solid from a components (benzoic remains solid
4. Filter
liquid (slow) acid and sugar) are
Residue: benzoic
more soluble in H2O acid
(sugar) and the other is Filtrate: sugar sol.
soluble in denatured
OH (benzoic acid)
Extraction Liquid-liquid Relative solubility - compound shaken 1. Sugar and Good extraction solvent:
extraction of components with 2 immiscible benzoic acid 1. immiscible with the sol.
solvents will distribute 2. Dissolve (heat) in to be extracted
itself between the 2
Solvent Separation: H2O 2. low boiling point for
solvents (2 layers will
extraction dissolving out of be formed: Organic 3. Cool to 30 deg easier removal
a component phase and aqueous 4. Pour to 3. dissolve the solute better
Most useful from a mixture phase) separatory funnel than the other solvent being
separation with a suitable - components go to the 5. Add methylene extracted
technique solvent solvent depending on chloride and stopper
their property, solute 6. Shake in an At a certain temp.
should be soluble to its
inverted position distribution coefficient K:
partner solvent
until 2 layers are
 formed conc .∈solvent 2
K=
7. Pour CH2Cl12 conc .∈solvent 1
layer and evaporate
in water bath It is more efficient to carry
out 2 extractions with ½ vol
of extraction solvent than
one large volume
Recrystalli Separation: Solubility and - Most organic 1. Dissolve impurity Good recrystallization
zation dissolved temperature compounds are more in a small amt. of solvent:
solute from soluble in hot solvents hot solvent 1. dissolve a moderate
- Impurities present will quantity of the substance to
its solution 2. Filter the boiling
have different be purified at high temps
solubilities from desired sol. but small quantity in low
compounds 3. Cool temps
- Charcoal is where 4. Mother Liquor- 2. not react with
impurities will stick filter crystals substances to be purified
- 3-5% more than the 5. Cool washing and 3. dissolves impurities
minimum is used so drying readily at a low temp or
that the hot sol. will not does not dissolve them at
be quite saturated all
- this helps prevent the 4. be readily removable
separation of crystals from the purified product
and clogging of the filter Failure to recrystallize
paper during filtration of remedies:
the hot sol. 1. seeding- adding small
crystal to induce crystal
growth
2. scratching- at inner
bottom wall to produce
rough surface
3. cooling- use dry ice by
 adding on mixture or as
bath
*still no
crystals=unsaturated sol.
so evaporate
*loss of crystals during
filtration=use vacuum
filtration

Sublimation Separation: High - Solid to gas to solid 1. Heating the solid - Often very clean products
Mixture of 2 volatility(vaporize - contaminants should in the presence of a are obtained and compared
solids where ) due to relatively not have the same clean cold surface to crystallization and is
properties
only one of weak 2. Molecules enter suitable for very small
- Impurities will be left
which can intermolecular the gas phase at amounts of sample
behind and pure
sublime forces high temperatures
substance will
and upon contact
evaporate and solidify
with the cold surface
at cool funnel
return to solid phase
- only one must sublime
as pure compound
- solids must have a
relatively high vapour
pressure below its
melting point
- Gentle heating must
be done to duly
increase the vapour
pressure
Thin-Layer Separation: Polarity of mobile - One can identify the Techniques: Can be used to:
Chromato Distribution phase and Affinity different components 1. Spotting the 1. Separate mixtures
graphy of the (strength of separated in a mixture plates 2. Identify compounds
mixture binding) of - different compounds - draw sample into 3. Determine how many
between two stationary phase will have different capillary tube (or components are present in
phases: solubilities and micropipette) a mixture
Stationary adsorption to the two - touch tip of tube on 4. Find out what solvents
and Mobile Development phases between which adsorbent 1 cm should be used for column
(developer) - interactions they are to be - spot must be chromatography
among partitioned above solvent level 5. Determine the purity of a
Ethyl acetate adsorbent, - different abilities of for sample not to be sample
hexane- developer and substances to adsorb or dissolved or wash
separate the spotted stick, to surfaces out during Good Chromatography
nonpolar compounds development Solvent should have good
- mechanisms: 1. Stationary phase - equally spaced resolution (separation):
Ethyl acetate 1. molecule is - thin layer of adsorbent spots, 1. ability to have different
acetic acid- bound to on a glass or plastic unoverlapped/ interactions with the
separate the adsorbent plate Overload different constituents no
polar 2. developer - relatively polar (Al2O3 - Score a small mark matter how similar the
attracts and silica gel) 2. Selecting a constituents are
desorbs it developer 2. usually a mixture of
3. developer 2. Mobile (developer - least polar solvent liquids
resides at site left phase) 3. Preparing the
by molecule to - in closed vessel as a development
prevent shallow pool of liquid chamber
readsorption solvent - small beaker
4. molecule is - capillary action: covered by watch
continually process in which it glass
adsorbed and ascends the slide within - may be lined with
desorbed the adsorbent solvent-saturated
(equilibrium) as -function: to selectively cylindrical paper to
solvent moves up desorb (remove from prevent evaporation
the plate the adsorbent) and - solvent 5mm depth
 5. if molecule is transport some then remove plate
more soluble in compounds farther than 4. Iodine chamber
solvent, it will others 5. Visualizing the
easily be pots
desorbed - UV exposure
6. if tightly bound - chemically
to silica, it will destructive method
spend more time
there

Thin-Layer Chromatography

Developer (mobile phase):

1. Polarity is a major consideration

-too polar: all material are carried about the same distance=poor separation

-too nonpolar: none of the compounds will be moved

Desorbing and transporting capability Polarity

Stationary phase:

Affinity/binding Distance travelled

The rate at which a compound ascends the thin-layer plate depends on the:

1. Polarity of the adsorbent

2. Polarity of the developing solvent

3. Polarity of the compound

Identities of compounds:

- Established by spotting known compounds with unknown sample

R f =d start ¿ center of substance spot ¿ ¿ solvent front ¿ ¿

¿ d start ¿
¿

Rf is very dependent on:

1. Moisture content (humidity)

2. Thickness of adsorbent

3. Purity of solvent

4. Other factors