ALCOHOL DETERMINATION

Introduction to Alcoholometry: Alcoholometry is defined as:

“Alcoholometry is the process or method of ascertaining the proportion of pure alcohol which
spirituous liquors contain”. or

“The term "alcoholometry" signifies the determination of the proportion of alcohol contained in a
liquid, whatever the nature of the liquid and whatever the method used”.

“Alcoholometry is the name given to a variety of methods of determining the quantity of

absolute alcohol contained in spirituous liquors”.

Ethyl alcohol is commonly known as alcohol. It is very widely used in pharmacy for various
purposes. It serves as vehicle in pharmaceutical preparations and manufacture of various
formulations. The amount and strength of alcohol used varies from preparation to preparation.
Thus determination of alcohol content is very routinely carried out in pharmaceutical industry.
Different methods are used for its determination.

ALCOHOLOMETRIC METHODS:

Different methods are used for the determination of alcohol in fluid extracts (a concentrated
liquid preparation, containing a definite proportion of the active principles of a medicinal
substance), tinctures (an alcoholic or hydro-alcoholic solution prepared from vegetable drugs)
and galanicals (any drug prepared from plant or animal tissue, especially vegetables, rather than
being chemically synthesized). Some of the methods used for measuring the alcohol content of a
liquid are discussed below:

1. Distillation Method Followed By Physical Measurement.

2. Distillation Method Followed By Chemical Analysis.
3. Boiling Method.
4. Ebulliometer Method
5. Gas Liquid Chromatography Method.
6. I.R Spectroscopy Method.

1. DISTILLATION METHOD FOLLOWED BY PHYSICAL MEASUREMENTS:

Traditionally, determination of alcohol in galanicals is carried out by distillation method

followed by physical measurements of the distillate. The basic principle of this method is the
distillation of the liquid sample using an appropriate distillation assembly. The distillate is then
analyzed either by determining specific gravity of distillate at specified temperature or by
refractive index. In distillation method care is to be taken to minimize the loss of alcohol by
evaporation.

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Most commonly the alcohol contents in the distillate are determined by specific gravity.
Standard alcoholometric table which relate specific gravity with percentage of alcohol by volume
or weight at different temperature are used to ascertain the contents of alcohol. Specific gravity
of distillate is determined by specific gravity bottle or more conveniently & quickly by
hydrometer. A hydrometer is an instrument used to measure the specific gravity (or relative
density) of liquids; that is, the ratio of the density of the liquid to the density of water.
Hydrometers may be calibrated for different uses, such as a lactometer for measuring the density
(creaminess) of milk, a saccharometer for measuring the density of sugar in a liquid, or an
alcoholometer for measuring higher levels of alcohol in spirits. Operation of the hydrometer is
based on Archimedes' principle that a solid suspended in a fluid will be buoyed up by a force
equal to the weight of the fluid displaced. Thus, the lower the density of the substance, the
farther (to a greater degree) the hydrometer will sink.

Hydrometer
Problems during distillation of alcohol from preparation: Following problems may occur
during the distillation process of alcohol from preparation:

Frothing: It is the formation of bubbles (foaming) in or on a liquid during the distillation

process. If the liquid gives frothing during distillation render it strongly acid with phosphoric,
sulfuric or tannic acid, or treat with a slight excess of calcium chloride solution to prevent
frothing. Frothing can also be prevented by the addition of a small amount of paraffin or silicone
oil before starting the distillation.

Bumping: It is a process in which a solvent becomes superheated and then undergoes a sudden
release of a large vapor bubble, explosively forcing liquid outside of a flask. Bumping can be
prevented during distillation by adding porous chips (called as boiling chips) of insoluble
material such as silicon carbide, or beads. Boiling chips are made of a porous material and have a
nonreactive Teflon coating - they provide nucleation sites (extremely localized budding for
gaseous bubbles) so the liquid boils smoothly/more easily. The air bubbles break the surface
tension of the liquid being heated and prevent superheating and bumping.

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Distillation Methods: Amongst distillation methods, the following methods are followed:

Method-I: For normal samples which do not need special treatment: This general method is
used for normal samples i-e which do not contain volatile impurities and interfering materials,
hence they do not need any special treatment before distillation. This method is again divided
into two separate methods, based on the type/ composition of the liquid to be distilled.

Method-I (a): For liquids presumed to contain less than 30% of alcohol:
 By means of pipette, transfer to a suitable distilling apparatus not less than 25ml of the
liquid in which the alcohol is to be determined.
 Add an equal volume of water (25 ml).
 Distil and collect a volume (23ml) of distillate about 2ml less than the volume taken of
the original test liquid.
 Adjust the distillate to the temperature at which the original test liquid was measured (i-e
room temperature).
 Add sufficient water (2 ml) to measure exactly to the original volume (25ml) of the test
liquid and mix. (2 ml + 23 ml = 25 ml).
 Determine the specific gravity of the liquid at 250C (room temperature).
 Determine the percentage, by volume of C2H5OH contained in the liquid examined by
reference to the standard alcoholometric table.

Method-I (b): For liquids presumed to contain more than 30% of alcohol:
 By means of a pipette transfer to a suitable distilling apparatus not less than 25ml of the
liquid in which the alcohol is to be determined.
 Dilute the test sample with about twice its volume of water. For a sample of 25ml, dilute
it with 50ml of water.
 Distil and collect the volume (48ml) of distillate about 2ml less than twice the volume of
the original test liquid.
 Adjust the distillate to the temperature at which the original test liquid was measured (i-e
room temperature).
 Add sufficient water (2 ml) to measure exactly twice (50ml) the original volume of the
test liquid and mix (2 ml + 48 ml = 50 ml).
 Determine the specific gravity of the liquid at 250C (room temperature).
 The proportion of C2H5OH, by volume, in the distillate, as ascertained from its specific
gravity, equals one-half that in the liquid examined. Multiply by 2 to get the percentage
of alcohol in the liquid examined.

Method-II: For samples which need special treatment: This method is used for the samples
containing appreciable amounts of volatile matter. The volatile matter gets into distillate during
distillation, and hence requires removal by special treatment before distillation.

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Special treatment for liquids containing volatile acids and bases: Determination of alcohol in
the samples containing volatile acids and bases, sample needs to be analyzed carefully. If the
sample containing alcohol is acidic (i-e if volatile acids are present), it should be neutralized with
sodium hydroxide solution and if alkaline (i-e if volatile bases are present) then neutralize with
sulphuric acid before distillation.

Special treatment for liquids containing 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., require special
treatment as follows:

For liquids presumed to contain less than 50% of alcohol:

 Mix 25ml of the sample, accurately measured, with about an equal volume of water in a
separating funnel (separator).
 “Saturate this mixture with solid sodium chloride”, then add 25ml of solvent hexane, and
shake the mixture to extract the interfering volatile ingredients.
 Draw off the separated, lower layer (aqueous saline layer) into a second separator, and
repeat the extraction twice with two further 25ml portions of solvent hexane.
 Extract the combined solvent hexane solutions with three 10ml portions of a saturated
solution of sodium chloride.
 Combine all the saline solutions, and distil in the usual manner, collecting a volume of
distillate having a simple ratio (1:1) to the volume of the original sample.

For liquids presumed to contain more than 50% of alcohol:

Adjust the sample to a concentration of approximately 25% of alcohol by diluting it with water
(i-e by the volume equal to twice the volume of the sample), and then proceed as directed in the
preceding paragraph, beginning with “Saturate this mixture with sodium chloride”.

2. DISTILLATION METHOD FOLLOWED BY CHEMICAL ANALYSIS:

This method is the same as for alcohol determination by distillation followed by hydrometry,
except that fewer amount of sample is required to be distilled and the alcohol concentration of
the distillate is determined by chemical means rather than hydrometry. Because the alcoholic
distillate can contain volatile acids and sulphur dioxide which can depress the hydrometer value,
resulting in false high alcohol determinations, the chemical analysis more exclusively targets the
alcohol contained in the distillate. This results in a truer more accurate measurement when
performed by an experienced analyst.
The chemical method utilizes potassium dichromate to react and convert the alcohol present in
the distillate to acetic acid, which is then titrated, under appropriate conditions, to an end point
and the alcohol concentration calculated.

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 3. BOILING METHOD :

The Boiling method can be used as a simpler, alternative method to the distillation method or to
confirm results obtained through the distillation and hydrometry method. This method follows
the distillation method, however, uses the difference in specific gravity of the sample before and
after the alcohol has been removed by boiling.
Procedure:
1. Measure the specific gravity of the sample by means of hydrometer and record the
measurement alongside the temperature the measurement was taken at.
2. Correct for the temperature difference between the recorded temperature and the
temperature the hydrometer was calibrated at, using the chart values for hydrometers
calibrated at 20oC, and record the true specific gravity of the sample as SG1.
3. Apply the distillation procedure to deprive the sample from alcohol by means of boiling.
4. Using a specific gravity hydrometer, measure the specific gravity of the alcohol depleted
solution and record your reading alongside the temperature the measurement was taken
at.
5. Correct for the temperature difference between the recorded temperature and the
temperature the hydrometer was calibrated at, using the chart values for hydrometers
calibrated at 20oC, and record the true specific gravity of the alcohol depleted solution as
SG2.
6. Using the equation below to calculate the alcohol concentration of the sample and record
the result.
Alcohol (% v/v) = (SG2-SG1) × 1000
Factor

4. EBULLIOMETER METHOD:

This method is based on the changes in the boiling point of the mixtures as a function of their
concentration. The Ebulliometer is a measuring device that is designed to evaluate the boiling
point of different types of liquids. Its use in the alcohol determination is based on the fact that
alcohol boils at 78.4 °C, a lower temperature than water, so the boiling point of alcohol-water
mixtures changes as a function of their concentration. Thus the method of ebulliometry takes the
advantages of the depression of the boiling point of water directly related to the concentration of
alcohol present in solution. The alcohol concentration level is determined by measuring the
difference between the boiling point of pure water at the prevailing atmospheric pressure and the
sample's boiling point, under the same conditions. Small differences in temperature (of the order
of 2-4 ºC per 1% v/v alcohol) occur, depending on the alcohol concentration.

A precision thermometer is involved, to determine the boiling temperature of the sample within
0.02 °C. The boiling point of any liquid depends on the atmospheric pressure, so the zero point

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has to be set against the boiling point of pure water prior to starting each test. The method is
fairly quick and sufficiently accurate for general purposes. However it is affected by atmospheric
pressure changes, a barometric change of 4 mm (during a test) would cause an error of 0.5 %vol.

5. GAS LIQUID CHROMATOGRAPHY METHOD:

Now-a-days gas chromatography is widely used in pharmaceutical analysis. This method is

adopted for certain specified samples containing alcohol. It gives accurate results rapidly.
Essentially, the gas chromatograph works by analyzing the mixture of organic compounds found
in the sample. The gas chromatograph has a series of filters made from porous materials.
Samples are injected by means of a syringe into an injector port on the device. The temperature
of the injector port must be in excess of the boiling point for the sample in order accurate
readings to occur. This allows the components of the sample to convert into gas, which then is
then pushed into the filters by way of helium or a similar carrier gas. As the sample gases pass
through the filters, the compounds are identified by electronic equipment and the alcohol content
is determined. While some models of the gas chromatograph feature a printer that creates a graph
of the progress of the sample, new models utilize a terminal display, making it possible to view
the results without having to decipher a graph.

6. I.R SPECTROSCOPY METHOD:

I.R spectroscopy determines the alcohol content in a highly alcohol-specific range. A highly
alcohol-specific range of the spectrum is identified between 1150 and 1200 nm. The evaluation
method uses the significant alcohol peak in this area and two spectral points very close to it for
defining the baseline. Extensive investigations showed that the alcohol results based on this type
of evaluation are virtually free of influences from other constituents. This allows adjustments to
be done simply with water for the zero point and one binary ethanol/water mixture. The
absorption information read by the detector array is used to determine the alcohol content of the
sample. A measurement is carried out in less than one minute.

Methods such as the combined density and refractive index method or Ebulliometer
determination tend to be inaccurate because the underlying measuring properties are non-specific
to alcohol. Traditional analysis methods such as distillation are time consuming and require
experienced operators. The accuracy of the above mentioned methods can be difficult to
maintain and repeatability is often at unacceptable levels. Compared to other methods GLC &
I.R methods are more accurate, sensitive and the results are reproducible.

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