Special Treatments

(Alcohol Determination)
Problems during Distillation
1) Frothing:
• Due to entrapment of air
• Foaming
• We can solve this issue by adding weak acid like phosphoric acid or tannic
acid.
• CaCl2 can also be used
• Addition of paraffin or silicon
2) Bumping:
• When large vapors/bubbles are formed with in the liquid and move towards
surface of boiling solution with high kinetic energy
• Add chips, balls or stones of CaCO3
Continued…
3) Azeotrop Formation
• It is a mixture of two or more liquids whose proportions cannot be altered or
changed by simple distillation.

4) Emulsification

5) Presence of Glycerin

6) Presence of Volatile substances

7) Presence of Iodine

• These problems require special treatment before distillation.

Glycerin
• Highly viscous and affect distillation process by altering specific gravity

• Do not increase the temperature to reduce the viscosity.

• To liquids that contain glycerin add sufficient water so that the

residue, after distillation, contains not less than 50% of water.
Volatile Acids and Bases
• Render preparations containing volatile bases slightly acidic with
diluted sulfuric acid before distilling.

• If volatile acids are present, render the preparation slightly alkaline

with sodium hydroxide solution

• Acidifying the bases or alkalinizing the acids causes them to be

converted to ionized form and make salts.

• These salts then do not interfere with ethanol evaporation in

distillation process.
Iodine
• Iodine is volatile

• Treat all solutions containing free iodine with powdered zinc before
the distillation, or decolorize with just sufficient sodium thiosulfate
solution (1 in 10), followed by a few drops of sodium hydroxide
solution.
Method B) Special procedure of Distillation where
volatile components are present
• Spirits, elixirs, tinctures, and similar preparations that contain
appreciable proportions of volatile materials other than alcohol and
water

• Examples include: volatile oils, chloroform, ether, camphor, etc.,

require special treatment
For liquids presumed to contain 50% of alcohol or
less
• Mix 25 mL of the test solution, with about an equal volume of water
in a separator.
• Saturate this mixture with sodium chloride
• Then add 25 mL of solvent hexane, and shake the mixture to extract
the interfering volatile ingredients.
• Draw off the separated, lower layer into a second separator
• Repeat the extraction twice with two further 25-mL portions of
solvent hexane.
Continued…
• Extract the combined solvent hexane solutions with three 10-mL
portions of a saturated solution of sodium chloride.

• Combine the saline solutions, and distill in the usual manner,

collecting a volume of distillate having a simple ratio to the volume of
the original specimen.
For liquids presumed to contain more than 50% of alcohol
• Adjust the test solution to a concentration of approximately 25% of
alcohol by diluting it with water
• Then proceed as directed in For liquids presumed to contain 50% of
alcohol or less, beginning with “Saturate this mixture with sodium
chloride.”

• If volatile oils are present in small proportions only, and a cloudy

distillate is obtained, the solvent hexane treatment not having been
employed, the distillate may be clarified and rendered suitable for the
specific gravity determination by shaking it with about one-fifth its
volume of solvent hexane, or by filtering it through a thin layer of talc.
C) Procedure for products which would cause
emulsification
• Proceed exactly as in Method A (Normal distillation) so that all the
volatile components are distilled off but the emulsifying agents
(surfactants) remain as residue
• After distilling up to approximately 90% of the sample, transfer the
distillate to a separator (without making the distillate up to volume)
• Add sufficient salt to saturate the liquid and add light petroleum
• Shake well and allow it to stand for two hours and proceed as in B
(Special procedure of Distillation where volatile components are
present)