Homework

 13.66 mg of a compound produced 10.71 mg of

carbon dioxide and 3.28 g of water. Another 4.86 g
of the same compound yielded 3.46 g of bromine.
The molecular weight is 673.72 g/mole.
 Calculate the percentages of carbon, hydrogen,
bromine, and oxygen in the sample.
 Determine
 the empirical formula
 the molecular formula
 the unsaturation number and its interpretation
 Separation of Mixtures
 Preliminary Test
 Will the sample survive the separation
procedure?
 Are the components of the mixture
stable under the conditions of the
procedure?
 Is this the easiest and most efficient way
to carry out the separation?
 Preliminary Test
 1. Note the physical state.
 solid is suspended in a liquid  remove the
solid by filtration and examine it separately.
 two immiscible liquids  separate and examine
them separately.
 2. Determine the solubility of the mixture
in water  Classify the mixture
 3. Liquid mixtures,
 evaporate 2 mL of the solution to dryness on a
watch glass note the presence or absence of
a residue.
 Apply the ignition test to the residue or 0.1 g of
the liquid or solid.
 4. liquid samples, determine the presence of water by
 (a) determining the miscibility of the solution with ether,
 (b) using the anhydrous copper sulfate test,
 add a small sample of anhydrous copper sulfate to the liquid.
 If the solution turns blue, it is indicative of the presence of water,
indicating the copper sulfate has absorbed the water.
 (c) using the distillation test for water.
 Place 5 mL of the liquid and 5 mL of anhydrous toluene in the
distilling flask of a distillation apparatus.
 Heat the mixture gently with a flame until distillation occurs.
 Collect 2 mL of the distillate.
 Add 5 mL of toluene to the distillate.
 The presence of two layers or distinct drops suspended in toluene
the presence of water.
 If the solution is only cloudy  traces of water.
 5. If water is absent determine the presence of a volatile solvent
 placing 1.0 mL of the mixture in a distilling flask in a simple distillation
apparatus. Place the distilling flask in a beaker of water and heat the water to
boiling.
 Any liquid that distills under these conditions is classified as a volatile solvent.
 Examine the distillate, which may be a mixture of readily volatile compounds,
and the residue in the flask separately.
 distillation of a water soluble mixture yields a volatile solvent and a water
insoluble residue removing all of the volatile solvent. The residue is
then treated as a water insoluble mixture.
 the residue after distillation is a water soluble liquid, do not remove the
solvent
 the residue after distillation is a water insoluble solid and the removal of
the solvent seems quantitative  remove all of the volatile solvent and
examine the distillate and the residue separately.
 If water is present, no such separation should be attempted.
 6. Determine the reaction of an aqueous
solution or suspension of the mixture to
litmus and to phenolphthalein.
 the mixture is acidic,
 titrate 1 mL (of a known exact weight) of the solution in
2.5 mL of water or ethanol with a standardized 0.1 M
NaOH solution to determine whether considerable
amounts of free acid are present or whether the acidity is
due to traces of acids formed by hydrolysis of esters.
 Perform the titration in an ice-cold solution, and take the
first pink color of phenolphthalein as the end point.
 Obtain an IR spectrum of a mixture to reveal the presence
of several carboxylic acid groups.
 7. Acidify 2 mL of the mixture with 5% HCl, and cool the
solution.
 Note the evolution of a gas or the formation of a precipitate.
 Add 5% sodium hydroxide solution to the solution until the solution
is basic and note the result.
 8. Make 2 mL of the mixture basic with 5% NaOH solution.
 Note the separation of an oil or solid, the liberation of ammonia,
and/or any color change. Heat the solution just to boiling and then
cool.
 Compare the odor with that of the original mixture.
 The presence of esters is often indicated by a change in odor.
 add 5% hydrochloric acid until the solution is acidic and note the
result.
 9. In the case of water insoluble
mixtures perform an elemental
analysis
 If water or a large amount of a volatile
solvent is present in a water insoluble
mixture do not perform the
elemental analysis
 If the water soluble mixture is
composed of solids perform an
elemental analysis.
 10. If water is absent, cautiously determine
the effect of
 (a) metallic sodium
 (b) acetyl chloride
 11. Determine the action of the following
reagents on an aqueous solution or
suspension of the original mixture:
 (a) bromine water
 (b) potassium permanganate solution
 (c) ferric chloride solution
 (d) alcoholic silver nitrate solution
 (e) fuchSin-aldehyde reagent
 (f) 2,4-dinitrophenylhydrazine
 Preliminary Test
 much information as possible is
deduced from the behavior of the
mixture.
 show the group in which the mixture
should be classified and
 indicate which of the following
procedures should be used in its
separation.
 DISTILLATION AND
SUBLIMATION

 .
 Distillation
 For amounts from a few milligrams to
5g
 Kugelrohr distillation apparatus

 For larger amounts up to 50 mL of
material short-path distillation
apparatus
 0.5-2.0 mL of a
sample
 Hickman-Hinkle
distillation
 microscale
distillation
apparatus
 fractional
distillation
apparatus
 compounds with a
difference in their
boiling points of 5-
100C or more can be
efficiently
separated.
 liquids and solids
of low volatility
which heat
sensitive vacuum
distillation
apparatus
 Steam distillation
 compound of relatively low
volatility can be purified by
co-distilling it with water.
 both of the liquid
components contribute to
the vapor pressure 
temperature slightly less
than 100°C at 760 mm Hg
(torr).
Solubility and Steam
Distillation
Rotary evaporator
(rotovap)
 removal of volatile
solvents
 Sublimation
 Sublimation is a
technique in which
a solid is heated
and vaporized,
without passing
through the liquid
phase.
 The gas is then
condensed and
collected as a solid
EXTRACTIONS : SEPARATIONS
BASED UPON SALT
FORMATION
 The separation of aniline
from toluene
 is effected by extraction with
dilute hydrochloric acid.
 The aniline goes into the
aqueous layer as its salt,
aniline hydrochloride.
 Whereas aniline is very soluble
in toluene and virtually
insoluble in water, its
hydrochloride salt, because of
its polar nature, is soluble in
water and insoluble in toluene.
 phenol from
toluene
 Mixture contains than 2
compounds????
 combinations methods of separations.
 The necessary condition for successful
separation is that :
the components be such that a wide
polarity difference exists or can be
induced between any two of them.
 Extraction of Water Insoluble
Mixtures
 These procedures
are used after the
water solubility test
 Assumption:
 all possible
fractions are
obtained
Extraction of Water Soluble
Mixtures
 If all components of the mixture
are water soluble, steam
distillation is the best method
for the separation.
 However, it may prove to be
unsatisfactory if the mixture is
not chosen carefully the
components of the mixture
undergo reaction with each
other or with boiling aqueous
acid or alkali during steam
distillation.
 Extraction, which does not
involve heating of the mixture,
would be preferable.
 EXAMPLE
 Sample:
 mixture of acetic
acid, butanol, butyl
acetate, water
 CHROMATOGRAPHY
 is the separation of the components of a mixture by
the selective distribution of the components between a
mobile phase and a stationary phase.
 Chroma meaning "color" and graphy meaning
"written“(Greek).
 The mobile phase
 is a liquid or a gas and carries the compounds along a column.
 The stationary phase
 may be composed of various types of materials,
 for example, silica gel in column chromatography.
 The ability to separate is based on selective and
preferential absorption of these components in the
mobile phase by the stationary phase.
 Organic chemists are interested in :
 gas chromatography (GC) and liquid chromatography (LC).
 Gas chromatography is useful for relatively volatile and
thermally stable organic compounds. This method involves
a gaseous mobile phase, which is usually helium or, less
frequently, nitrogen. The stationary phase is either a liquid
adsorbed on a solid support, an organic compound bonded
to a solid support, a solid, or a nonvolatile liquid.
 Liquid chromatography uses a liquid mobile phase, which is
usually a common organic solvent. The stationary phase
may consist of a liqUid adsorbed onto a solid support, an
organic species spread over a solid support, a solid, or a
resin. Examples of liqUid chromatography are column
chromatography, high-performance liquid chromatography
(HPLC), and thin layer chromatography (TLC).
 Choosing GC or LC?
 Gas Chromatography
 1. The sample should be volatile and reasonably stable to heat.
 2. Simple gas chromatographs are inexpensive, are easy to operate, and give
results rapidly.
 Liquid Chromatography
 1. Duration: With the simple gravity flow columns, the separation of the
components is time consuming.
Rapid analyses are carried out with HPLC and flash chromatography.
 2. Stability: A small percentage of organic compounds may react with the
stationary phase of some columns.
Proper choice of conditions, in order to prevent undesirable side reactions,
allows virtually any organic compound to be analyzed by LC.
 3. Cost: Flash and other types of column chromatography are fairly cheap;
HPLC has a much higher initial cost, because of the high-quality pumps and
column packings that are necessary.
 Thin-Layer
Chromatography
 the most rapid, easiest, and
most often applied method
for accessing Organic
compounds.
 the immobile phase is a thin
layer of adsorbent spread
over a sheet of glass or
plastic
 Compounds can be detected
on TLC sheets in various
ways. The simplest is to use
a low-power hand-held UV
light.
Procedure