ALCOHOL DE-

TERMINATION
PRESENTED TO: MISS NAYAB NAEEM
PRESENTED BY:
RIMSHA SHAFIQUE
RUHMA ZAHID
MUSHAIDA IMRAN
MUHAMMAD ISMAIL
SUBHAN ALI
Outlines

1 Alcoholometric methods.

2 Problem during distillation of alcohol.

Method for liquid containing less than 30% or more than

3 30% alcohol.

4 Special treatment before distillation.

 What is alcohol determination?
“The measurement of percentage of alcohol in different dosage forms.”
Properties of Alcohol:
Alcohol means ‗ethanol‘, used in preparations because of its important
properties:
 Used as solvent.
 As co-solvent along with water.
 Used because of its preservative properties.
 Nontoxic in nature.

Alcoholometric methods:
Officially TWO methods are used:
A). Distillation Method.
B). GLC Method.
 Method I (Distillation Method)
Before distillation, some “precautions” must be observed as:
 Distillate should be clear. If it is cloudy, treat with Talc or some other
material like CaCO3.
 Finely filtered it.
 Temperature of distillate should be adjusted to temperature of the sample.
 Alcohol loss during distillation should be avoided.
 Distillation flask should be an appropriate size i.e. 3 to 4 times bigger in
volume than sample.
 Distillation method
 Distillation method is to be used for determination of alcohol unless otherwise
specified in individual monograph.
 It is suitable for examining fluid extracts, tinctures, provided the capacity of the
distilling flask is sufficient (commonly 2 to 4 times the volume of the liquid to be
heated) and the rate of distillation is such that clear distillates are produced.

Procedure:
Two types of procedures are there:
1. Distillation Method for Liquids presumed to contain less than 30% v/v Alcohol.
2. Distillation Method for Liquids presumed to contain more than 30% v/v Alcohol.
Distillation Method for Liquids presumed to contain less than 30% v/v alcohol.
Following procedure is adopted:
o 25 ml of sample + equal volume of distilled water.
o Distill the resultant.
o Distillate should be 2 ml less than the original volume i. e. 23 ml.
o Add water to make up 25 ml.
o Adjust temperature of distillate to the temperature of sample.
o Find out specific gravity or refractive index of the distillate.
o From Alcohol metric Table, find out the %age of alcohol (v/v).
Distillation Method for Liquids presumed to contain more than 30% v/v Alcohol
Following procedure is adopted:
o 25 ml sample + 50 ml of distilled water.
o Distillation
o Distillate should be 2 ml less than the 50 ml i. e. 48 ml.
o Add water to make 50 ml.
o Adjust temperature of distillate to the temperature of sample.
o Determine specific gravity or refractive index of the distillate.
o Find out the %age of alcohol from Alcohol meter Table.
o The proportion of alcohol by volume equals ½ of that in the liquid
examined. There fore, multiply it with “2” to get exact per cent of
alcohol in the sample.
METHOD II (GAS LIQUID CHROMATOGRAPHY)
USP Reference Standards
1. USP Alcohol Determination—Acetonitrile RS
2. USP Alcohol Determination—Alcohol RS.

Apparatus
Gas chromatography specification
3. Flame-ionization detector
4. Nitrogen or helium as the carrier.
Temperature specification
5. Prior to use, condition the column overnight at 235oC with a slow
flow of carrier gas.
2. The column temperature is maintained at 120◦C
3. The injection port and detector temperatures are maintained at 210◦C.
4. Adjust the carrier flow and temperature so that acetonitrile, the internal standard,
elutes in 5 to 10 minutes.
Solutions
Test Stock Preparation:
Dilute the specimen under examination stepwise with water to obtain a solution
containing approximately 2% (v/v) of alcohol.
Standard Preparation:
Pipet 5 mL each of the USP Alcohol Determination—Alcohol RS and the USP
Alcohol Determination— Acetonitrile RS [Alternatively, a 2% aqueous solution of
acetonitrile of suitable quality may be used as the internal standard solution] into a
50-mL volumetric flask, dilute with water to volume, and mix.
Procedure:
 Inject about 5 µL each of the Standard Preparation, in duplicate, into the gas
chromatograph, record the chromatograms, and determine the peak response ra-
tios.
 Calculate the percentage of alcohol (v/v) in the specimen under test according to
the formula:
CD(RU / RS)
o C is the labeled concentration of USP Alcohol Determination—Alcohol RS
o D is the dilution factor (the ratio of the volume of the Test Stock Preparation to
the volume of the specimen taken);
RU and RS are the peak response ratios obtained from the Standard Preparation,
 Problems during Distillation of Alcohol
Following problems may occur during distillation of alcohol:
1. Frothing / Foam Formation:
 The foam formation in the distillation flask is frothing due to presence of
surface active agents.
 It may cause problem in accurate measuring.
Remedy:
 Treat with slight excess of CaCl₂ solution.
 Addition of small amount of paraffin oil or silicone oil before starting distillation.
2. Bumping:
 Bubble formation in distillation flask is called bumping.
 It may exert pressure on the walls of vessel which may break the vessel.
Remedy:
 It can be prevented by adding porous chips of insoluble material e.g., silicon
carbide, glass chips, beads.
3. Cloudy / Milky Distillation
Cause problem in measuring.
Remedy:
Clarification is done by adding talc or calcium carbonate, chalk and then filter.
4. Azeotrope Formation
 Complex formation between two agents which may change the nature of
individual components is called Azeotrope.
 Azeotropes are also called constant boiling mixtures.
 They are binary mixtures having the same composition in liquid and vapor
phase and boil at a constant temperature. In such a case it is not possible to
separate the components by fractional distillation.
Example: Water+ acetonitrile (Azeotrope formation)
5. Emulsification:
It can be problematic for the process of distillation.
Remedy:
 Distillate is saturated with brine and light petroleum.
 Excessive temperature can break emulsion.
Special Consideration
a) Volatile Acids & Bases:
If preparations contain volatile bases make it slightly acidic with diluted sulfuric acid
before distilling. If volatile acids are present make the preparation slightly alkaline
with sodium hydroxideTS.(4% NaOH)
b) Glycerin:
If sample contain glycerin add sufficient water so that the residue, after distillation,
contains not less than 50% of water.
c) Iodine:
If the sample solution contain free iodine than treat sample with powdered zinc
before distillation. OR Decolorize with just sufficient sodium thiosulfate solution
(1in10), followed by a few drops of sodium hydroxide TS.
d) Other Volatile Substances:
Spirits, elixirs , tinctures, and similar preparations that contain appreciable
proportions of volatile materials other than alcohol and water, such as volatile oils ,
chloroform , ether , camphor , etc.,
Thank you