Special Treatments

• Volatile acids and bases

• Render the preparations containing volatile bases
slightly acidic with dilute sulphuric acid before
distillation
• If volatile acids are present, render the preparation
slightly alkaline with sodium hydroxide test
solution
• Acidifying the bases or alkalinizing the acids
causes them to be converted to ionized form and
form salts. These salts then do not interfere with
ethanol evaporation in distillation process.
• Glycerin and iodine
• Glycerin: To the preparation containing
glycerin, add sufficient water so that after the
distillation, the residue contains not less than
50% of water.
• Iodine: Solution containing free iodine must be
treated with;
– 1- Powdered zinc (zinc iodide will be formed)
– 2- Decolorize with sufficient sodium thiosulfate
solution followed by few drops of sodium
hydroxide
• Other Volatile substances
• Spirits, elixirs, tinctures and similar preparations that contain
appreciable proportion of volatile materials other than alcohol
and water such as volatile oils, chloroform, ether, camphor, etc
• For liquids presumed to be containing 50% alcohol or less
• Mix 25ml sample with equal volume of water in a separator
• Saturate with NaCl & add 25ml hexane and shake well to remove
any interfering volatile substances
• Draw off the separated lower layer into a second separator and
repeat the extraction twice with hexane (2, 25 ml portions)
• Extract the solution (combined solvent hexane ) thrice with 10ml
portions of saturated saline solution
• Combine all these portions and distil as usual
• Take volume having simple ratio to original specimen
• For liquids presumed to be containing more
than 50% alcohol
• Adjust the conc. of alcohol to approximately 25%
v/v by diluting with water.
• Perform the same procedure as above beginning
with “saturate this mixture with sodium chloride”.
• If volatile substances are in small portion.
Shake distillate with about one-fifth its
volume of solvent hexane, or filter it through a thin
layer of talc
 Gas-liquid Chromatographic
Methods
• Now-a-days gas chromatography is widely used in
pharmaceutical analysis. This method is used for
certain specified samples containing alcohol. It gives
accurate results rapidly.
• Principle
• This technique is based on the partition of molecules
between the two phases i.e. mobile phase and stationary
phase.
• The mobile phase is gas, most often Helium (nitrogen).
• The stationary phase is usually liquid and may be;
– Polyethylene glycol for separation of polar compounds.
– Polymer of silicon for separation of non-polar compounds.
• Apparatus
• The apparatus consists of:
• Injector
• Detector
• Retention time (RT) data analyzer
• Procedure
– Two standard solutions of Ethanol are prepared
• Liquid containing more than 10 % alcohol
• For its detection two standards are used:
– Standard-I containing 5 % more alcohol (Ethanol) than the
sample.
– Standard-II containing 5 % less alcohol than the sample.
• Liquid containing less than or 10 % alcohol
• For its detection, the standard used is:
– Standard-I containing 1 % more alcohol than the sample.
– Standard-II containing 1 % less alcohol than the sample.
 Standard Solutions

Samples presumed to Samples presumed to

contain more than 10 % contain less than or equal to
alcohol 10 % alcohol

SS-I containing 5% SS-II containing SS-II containing SS-I containing 1%

more alcohol than 5% Less alcohol 1% Less alcohol more alcohol than
presumed than presumed than presumed presumed
• Procedure
• Take 25 ml of each standard and sample solution in a
container bearing stopper.
• Add 10 ml of internal reference solution of Acetone.
• Use flame ionization detector, Carbowax as stationary
phase, Helium as mobile phase and column of 2-4 mm
dimension.
• Set the flow rate at 30 ml/sec.
• Maintain the injector temperature at 210°C, detector
temperature at 150°C and column temperature at
120°C.
• Inject 2 µl for each solution five times and note the
retention time.
• Calculate the %age of alcohol from the following
formula:
• % alcohol = S1 ( Y – Z ) + S2 ( Z – X )
• Y–X
• S1 = % age of alcohol of standard-I.
• S2 = %age of alcohol of standard-II.
• X = Ratio of RT of the internal reference solution to the
RT of standard-I.
• Y = Ratio of RT of the internal reference solution to the
RT of standard-II.
• Z = Ratio of RT of the internal reference solution to the
RT of sample solution.
• Ratio = peak area of sample/peak area of acetone