ALCOHOL

The alcohols are the hydroxyl derivatives of hydrocarbons. They are

theoretically obtained by replacing one or more hydrogen atoms from the
hydrocarbons by hydroxyl groups (OH).
Classification –
Depending on the no. of OH groups present in its molecules
1. Monohydric alcohol :
The general formula of saturated monohydric alcohols is C nH2n+1OH
or briefly R-OH. The -OH is obviously the functional group of alcohols.
They are primary, secondary or tertiary according as the -OH group is
attached to a primary, secondary or tertiary carbon atom.
i) Primary alcohol - Contain -CH2OH group and they may be
represented by the general formula R.CH2OH. e.g. H-CH2OH
(methyl alcohol) ; CH3- CH2OH (ethyl alcohol).
ii) Secondary alcohol - contain > CHOH group and they may be
represented by the general
Formula R1 CHOH
R2
E.g CH3 CHOH ( Isopropyl Alcohol)
CH3
CH3 CHOH ( Secondary Butyl Alcohol)
CH3
iii) Tertiary alcohol - contains C-OH group and they may be represented by the
general formula
R1
R2 C-OH
R3
 e.g CH3
CH3 C-OH ( T-butyl Alcohol)
CH3

2. Di-hydric Alcohol -
Alkaneols or glycols contain two hydroxyl groups on different carbon atoms.
The simplest, methylene glycol, CH2(OH)2, is unknown in the free state; an
aqueous solution of formaldehyde, HCHO, is believed to exist as methylene
glycol. 1, 2 - or vicinal glycols are the most important. Ethylene glycol or ethane
-1, 2 - diol, CH2OH—CH2OH, is the first representative number of the series.
Glycols have the general formula CnH2nOH)2 The common names of 1, 2 - glycols
are obtained from the corresponding alkene by adding 'glycol' to it, e.g. propylene
glycol, CH3—CHOH—CH2OH.

3. Tri-hydric alcohol :
CH2OH

CHOH (glycerol)

CH2OH

ETHYL ALCOHOL
Chemical formula : C2H5OH
Molecular weight : 46.07
Synonyms: Ethanol; Spirit of wine; Grail alcohol.
Sources :
1. Molasses, a waste byproduct from sugar factories. In India, it is the main source
of ethyl alcohol.
2. Substances rich in starch (C6H10O5, e.g. rice, wheat, maize, potato etc
3. Substances rich in sugar, e.g. beef carrot, grapes, sugarcanes etc.
4. From sugars, e.g. beet-sugar, cane sugar etc.
5. Synthetically - from ethylene.
Preparations :
A. From Molasses -
Molasses is the mother liquor left and crystallization of cane-sugar from
cane juice It contains about 50% fermentable sugar (sucrose, glucose, fructose). It is
a thick dark coloured liquid. It is the chief source for manufacturing of alcohol.
The various steps involves are —
(a) Preparations of Wash -
1) Molasses is diluted with waste to prepare a 10% solution sugar. A small
amount of (NH4)2S04 is added to it as a food for the ferment. It is acidified
with small amount of H2S04.
2) It is warmed at 25°C - 30°C and yeast ferment added to it.
3) Fermentation starts with the evolution of C02 and is completed in 2-3
days.
4) The enzymes invertase and zymase present in yeast bring about the
decomposition of cane sugar into ethyl alcohol as follows :
C12H22O11 + H2O invertase C6H12O6 + C6H12O6
C6H12O6 Zymas 2C2H5OH + 2CO2
The fermented liquor is known as 'wash'.
(b) Distillation of Wash -
The wash contains 15% alcohol. It is subjected to fractional
distillation in a special type of fractionating column known as Coffey's still.
The vapours of almost pure alcohol from the head of the fractionating
column are lead to the condenser The distillate so obtained is known as
crude rectified spirit and contains about 95% v/v or 92% w/w of ethyl
alcohol.
Process : It consists of the following steps —
1. Sachharification : The process of converting starch into maltose
is known as Sachharification.
It consists of the following steps –
 Malting : Barley is allowed to germinate in the dark, at 15°C,
when enzyme diastase is developed in it. After a few days
germination is stopped by the action of heat and the malt so
obtained is extracted with water. The malt extract contains
diastase in solution.
 Mashing : Suitable starchy material is suspended in water and
agitated with superheated steam under pressure to get a pasty
mass. This suspension of starch is known as 'mash'.
 Hydrolysis : Mash is mixed with malt extract and the
temperature maintained between 50°C to 60°C. Fermentation
starts and, under the influence of diastase, starch is, hydrolysed
into maltose.
2. Alcoholic fermentation :
The solution of maltose so obtained is mixed with yeast at 30°-35°C
and kept for 3-4 days. Maltose is converted into glucose by the enzyme
maltose contained in the yeast. Glucose is converted to C 2H5OH and C02, by
the enzyme zymase contained in yeast. A 15% solution of C 2H5OH is
obtained by this process, and technically known as 'wash'. It is subjected to
fractional distillation in a special type of fractionating column known as
Coffey's still. The vapours of almost pure alcohol from the head of the
fractionating column are lead to the condenser. The distillate so obtained is
known as crude rectified spirit and contains about 95% v/v or 92% w/v of
C2H5OH.
Properties of alcohol :
1. It is a colourless, neutral, transparent volatile liquid (boiling point
78.5°C) with a pleasant smell and burning taste.
2. It is lighter than water (Sp. Gr. 0.789)1 and miscible with it in all
proportions! with evolution of heat and contraction! in volume.
3. It freezes at -114°C and so it is used! in 'alcohol thermometer' fool
measuring low temperatures.
4. It is highly hygroscopic and inflammable; it burns with a pala blue
smokeless flame.
5. In small doses, alcohol is a stimulant! but, in excess, a poison.
6. Alcohol is a good solvent for organic! compounds.

Advantages of alcohol :
1. Non-expensive, as it is prepared from waste product—'molasses'.
2. It has no medicinal property of its own.
3. Neutral in reaction, i.e. neither acidic nor alkaline.
 4. Not spoiled by long storage.
5. Soluble with almost all common fluids.
6. Edible in small doses, acts as a stimulant and is non-poisonous.
7. Preparation is not much difficult.
8. It possesses great extracting power for the medicinal properties front
crude and mucilagenous substances,
9. At 70% strength, it acts as a great preserver of animal and plant
tissues
10.It is used in increasing strengths for dehydration of animal and plant
tissues.

Disadvantages of alcohol :
1. It evaporates easily. So it should be kept in air-tight bottles.
2. Highly inflammable, if kept near fuel So it should be kept in cool
place! away from fire, with fire-fighting arrangements.
3. Ordinary corks are easily discoloured if come in contact with alcohol
by overfilling the bottle.
4. It is a highly taxable item.
5. Not easily procurable, as it is strictly controlled by every Govt's Excise
Departments.
6. It cannot dissolve many inorganic salts directly. Albuminous and
starchy substances are not dissolved in alcohol.
7. In large doses it is poisonous.
Precautions in preserving or using alcohol :
1. It must be stored in cool dark place and in air-tight closed container - as
it evaporates easily and absorbs moisture from atmosphere or air.
2. Bottles made up of pyrex glass (81%, Si0 2 ; 5% Na20 ; 2% A1203 ; 12%
 B203) should be preferred. Bottles must be well-cleansed.
1. Alkaline bottles should be avoided.
3. It is highly inflammable. So it should be kept in cool place away from
fire, with fire-fighting arrangements.
Uses of alcohol :
1. It is added to the juice of plants in fresh state, to prevent their
deterioration (Sec. 267 Organon of Medicine). It also prevents moulds,
yeast and fermentation of materials inside.
2. For preparing mother tinctures (Class I to Class IV under old method)
and mother solutions (Class VI) from crude drug materials.
3. For preparing dilutions and higher potencies.
4. It is easy to prepare medicines and medicate globules with alcohol
5. It is used for preparing medicines from gums, resins, oleo-resins, resi-
noids, alkaloids and many volatile oils.
6. It is employed for making methylated spirit (for varnishes, lacquers
etc.), ether, ethylene, chloroform, iodoform, acetic acid, etc. and
also for transparent soaps, hair washes.
7. It is a solvent in the dye and rayon I industries.
8. Ethyl esters make fruit essences and perfumes.
9. It works as an anti-septic, at a strength of above 10%
10. It has a cooling effect and so applied on burns and over forehead to
soothe burning sensation and headache, respectively.

The Food value of alcohol :

The alcohol may be regarded as a food, within certain limit. The chief
point is whether it can be regarded as a protein sparer.
The proteins help in formation and repair of tissues. Carbohydrates
and fats are sources of heat and energy. Since alcohol does not contain any
nitrogen, it cannot replace protein and, therefore, has no power to build
tissues. Whereas about 90% of alcohol taken disappears in the body and is
converted into C02 and water; by virtue of the chemical energy thus liberated
can replace carbohydrate and fats in the diet and in this sense it is a non-
nitrogenous food
But, when taken with other foods, ill economizes the use of fat and
carbohydrate, which, in their turn, are stored in the body, the carbohydrate as
glycogen and fat in tissues. As alcohol does not require digestion it is in a
sense superior to other foods Moreover, it does not require more energy I for
absorption than other foods.
Though it cannot replace protein, alcohol will, under certain
conditions, spare the protein in the same way as fat and thus prevent tissue
waste. Alcohol, therefore, is regarded as a food in the sense that it will when
given with other foods, replace carlbohydrate and fat for a short time and
would supply energy and spare protein and prevent tissue waste. But the
value of alcohol as a food is limited because the supply of energy is fixed
and cannot be adjusted according to the needs of the body nor can it be
increased to meet sudden emergency, because it cannot be stored in the body
like fat or carbohydrate as reserve.
The caloric value of alcohol in diet lies in between carbohydrate (4.3
cal/gm) and fat (9.3 cal/gm) whereas alcohol supplies 7 calories—as such, a
pint of whisky will supply 1,400 calories (approx).
IMPURITIES OF ALCOHOL :
1. Various kinds of impurities :
(a) Fusel oil : It is the commonest impurity in alcohol. It is a bright
yellow liquid (from the last runnings in the distillation of crude spirit), is
chiefly iso-amyl alcohol or iso-butyl carbinol, (CH3)2CH—CH2—CH2OH,
(boiling point -131 °C) with traces of two propyl alcohols, butyl alcohols,
some esters etc.
Fusel oil comes from the amino-acids such as valine and leucin
present in starch.
(b) Acids e.g. succinic acid.
(c) Water (H20).
(d) Other inferior qualities of alcohol : Amyl alcohol, Propyl alcohol, Butyl
alcohol ; Glycerine.
(e) Aldehydes and Ketone bodies : e.g. Acetaldehyde.
3. Method of removal of impurities (purification of alcohol) :
After detection of impurities in alcohol (such as fusel oil, aldehyde,
ketone, water, low quality alcohol etc.), the impure alcohol is purified by
distillation with purified animal charcoal.
CHIEF VARIETIES OF ALCOHOL
Alcohol

Absolute Strong Dilute Dispensing Rectified

alcohol alcohol alcohol alcohol spirit
(Sp. Gr : (Sp. Gr : (Sp. Gr : (Sp. Gr :(Sp. Gr :
0.792, at 0.816 at 0.89 at 0.840 at 0.812 at
15.6'C) 15.6'C) 15.6'C) 15.6'C) 15.6'C)
Absolute Alcohol :
1. Synonyms : Anhydrous alcohol; Alcohol dehydrated.
2. Definition : By the term 'Absolute alcohol' is meant alcohol entirely free
from water, i.e. 100% pure alcohol. Strictly, this is an incorrect name, for it
may contain 1 per cent by weight of water.
Theoretically it is 100% of ethyl alcohol (C2H5OH) by volume (v/v) or
by (w/w) but, practically, it contains not less than 99% by weight of ethyl
alcohol (C2H5OH) and not I more than 1% water.
3. Specific gravity : At 15.6°C or 60'F,| 0.792.
4. Preparation of absolute alcohol - Absolute alcohol can be prepared
in two ways :
(a) Rectified spirit (R.S.) + Fresh quid lime (CaO)

Heated, due to which most of water is removed.

Distillation.

Distillate now contains about 0.6 to 1% I water - so to remove the traces of

water

Refluxed over metallic calcium (Ca)or magnesium (Mg).

Re-distillation, in an all-glass apparatus.

Redistillate.

First & last portion Middle portion

(Rejected)
Collected which is pure and unmixed
(b) On the large scale :
Rectified spirit mixed with little Benzene (C6H6).

Distillation

Distillate

First fraction Second fraction Last fraction

Contains constant Contains constant Contain pure

boiling mixture of boiling mixture of anhydrous alcohol
C2H5OH, H20 & C2H5OH & C6H6 (B.P : 78.5'C) &
C6H6 (18.5% + (32.4% + 67.6%) is known as
7.4% + 74.1%) B.P - 68.2’C absolute alcohol.
B.P - 64.8"C

Difference between absolute alcohol and homoeopathic alcohol :

The homoeopathic alcohol is of 87% strength and is used in making
homoeopathic attenuations. Absolute alcohol, theoretically, should be 100%
proof. Practically 95% is about the highest it ever attains, as it constantly
absorbs water from the atmosphere. 95% alcohol may be reduced to
homoeopathic alcohol by adding to 7 parts of 95% alcohol 1 part of purified
water.

6. Purity test of absolute alcohol :

As regards the traces of water (0.3%), 10 ml. of the sample of alcohol
is taken in a test tube and vigorously shaken with 0.5 gm of anhydrous
copper sulphate, which will turn blue, if water is present in the sample.
7. Uses: It is used in Stapf process for the purification of Sugar of milk.

Strong Alcohol :
1. Synonyms : Alcohol fortior ; Alcohol fortis.
2. Definition : In homoeopathy, when the word alcohol only used it
means strong alcohol This is obtained after second distillation
and its strength becomes appr. 95% by volume.
3. Preparation : It is prepared by mixing 94.9 p.c. by volume of pure
ethyl alcohol (C2H5OH) and 5.1 p.c. by volume of purified water; It
may be diluted to any extent with purified water
4. Properties :
 Specific gravity : At 15.6°C or 60T, 0.816,
 Refractive index (nD20) : 1.3637 to 1.3639.
 It is colourless, mobile volatile pleasing aroma and burning
taste.
 It is neutral to all indicators when pure.
 It is miscible with purified water, acetoneT (CH3—CO—CH,),
chloroform (CHC13), ether and many_other organic solvents.
 Iodoform test : Take 2-3 ml of The solution in a test tube, add
equal volume of a strong solution of iodine in potassium iodide,
warm gently, take it out the flame and add a solution of NaOH
drop by drop until the colour is pale yellow. Cool the test tube,
a, yellow crystalline ppt. of Iodoform Separates out
C2H5OH + 4I2 + 6NaOH = CHI3
+ HCOONa + 5NaI + 5H20.
 5. Uses –
 It is used for the preparation of mother tinctures from
vegetable and animal substance under Hahnemannian old
method as well as in new method.
 For the preparation of mother solutions (i.e. alcoholic
solutions) as in Class VI under old method, where the drug
substance is soluble in alcohol.
 For the preparation of absolute alcohol. dilute alcohol and
dispensing alcohol.
 Storage : It should be kept in well stop pered glass bottle in
cool dark from fire as it is very inflammable
Dilute Alcohol :
Different authorities differ as regards the specification of dilute alcohol :
1. As per H.P.I. (Vol I) : Dilute alcohol (66%) contains 62.5% v/v or
60.6% w/w of alcohol. Dilute 695 ml of strong alcohol to 1,000 ml with
purified water. Specific gravity: At 20°C, 0.9139 to 0.9169.
2. As per A.H.P. : It consist of, 7 parts of alcohol (Sp. Gr : 0.83) and 3
parts of purified water. Specific gravity : At 15'C, 0.89.
3. As per B.H.P. : It consist of equal quantity of rectified spirit, 60 o.p and
purified water.
4. As per M. Bhattacharya's pharmacopoeia : 7 parts in volume of
rectified spirit 60 o.p is added to 3 parts in volume of purified water.
Specific gravity : 0.89.
5. As per Drs. Buchner, Gruner, Jahr, J. Hantpel: It is prepared by adding
equal parts in volume of alcohol and purified water.
6. As per Dr. K. P. Majumder :
a. It is prepared by adding 7 parts of alcohol (Sp. Gr : 0.816) with
 3 parts of purified water in volume. Specific gravity : 0.935 to
0.937.
b. Equal volume of strong alcohol (Sp. Gr : 0.816) and purified
water (for official dilute alcohol).
7. As per Dr. Dewey : It is prepared by adding 7 parts of 87% alcohol wil
3 parts of purified water.
Note : When alcohol is mixed with purified water there is rise of
temperature with shrinkage in volume to an extent of 3%. Sol little more
purified water should be added to make the specific gravity stand at 0.89.1
8. Uses :
 For the preparation of potencies, I particularly under decimal scaler
 For cleansing of utensils.
Dispensing Alcohol :
1. Synonyms: Alcohol officinalis, officiall alcohol.
2. Definition : It contains 88% by volume or 83.1% by weight of ethyl
alcohol (C2H5OH) and 12% by volume oil purified water.
3. Preparation : It is prepared by mixing :
 10 parts by weight of strong! alcohol (Sp. Gr : 0.816) and 1 party by
weight of purified water. Oil
 12.25 parts by volume of stronge alcohol (Sp. Gr : 0.816) and ll par t
by volume of purified water
The specific gravity of the resulting j dispensing alcohol, at 15.6°C or
60°F is O.840

4. Uses : It is mostly used for potentising the drugs from their mother
tincturel state, as it is more readily absorbed by globules, sugar of milk or
tablets
Rectified spirit (60° O.P.) :
Definition : Rectified spirit 60" o.p. means that 100 volumes of the
alcohol, diluted with purified water, will give 160 volumes of proof-spirit.
In other words, it means pure rectified spirit contains 160 per cent of proof-
spirit.
It contains 91.29% by volume of C2H5OH having specific gravity at
15.6°C is 0.8294.
Preparation : It is prepared by mixing 375 ml. of purified water with 1,000
ml of strong alcohol.

2. Uses :
 It is used for potentisation of medicine under centesimal scale.
 For cleansing of utensils.

Q. State the type, strength, source and common impurities of alcohol

generally Indian pharmacists are supplied.
Type : Rectified spirit.
Strength : 60° o.p.
Source : Molasses
Common impurity : Fusel oil.
Rectified spirit (40° O.P.) :
It is prepared by mixing 7 parts of strong alcohol with one part of purified
water, both by volume. It contains 73.37% by weight of strong alcohol, Sp.
Gr. 0.8646 at 15.6°C.
Rectified spirit (20° O.P.) :
It is prepared by mixing 6 parts of strong alcohol with 2 parts of purified
water, both by volume. It contains 60.85% by weight of strong alcohol. Sp.
Gr : 0.8936.
Denatured spirit (Alcohol) -Methylated spirit :
Alcohol is largely used as solvent and also as intoxicating drinks. To make it
unfit for unlawful human consumption, poisonous or bad smelling
substances are mixed in small quantities with the rectified spirit. The
mixture is known as denatured spirit. The substances usually mixed for this
purpose are methyl alcohol, benzene, bone oil, crude pyridine and
caoutchoucine etc. The product is also slightly coloured by adding some dye
to indicate its nature. This, however, does not prevent its use as a solvent in
industries.
Rectified spirit, denatured by mixing methyl alcohol, is known as
methylated spirit. Nowadays, however, 0.5% light caoutchoucine (obtained
by distilling vulcanised rubber) and 0.5% pyridine bases of are used as
denaturants, although the old name (methylated spirit) is still used.
Proof-spirit (Alcoholometry) :
Definition : Proof-spirit is defined by Act of Parliament as : "being such as
12
shall, at a temperature of 51°F, weighs exactly /13th part of an equal
measure of purified water". In other words, proof-spirit is a mixture of
alcohol and purified water, weighing 12/13th of an equal volume of purified
water at 51 °F.
Standard strength : The proof-spirit is 57.1% of ethyl alcohol (C2H5OH) by
volume or 49.28% of C2H5OH by weight and 42.9% of purified water by
volume with specific gravity 0.91976 at 60°F.
It is fixed by the Excise Department and is measured by a special type
of graduated hydrometer (i.e. alcohol hydrometer).
Designation : This spirit of standard strength (i.e. proof-spirit) is expressed
in terms of degrees under or over-proof.
The alcohol which is stronger in strength than this proof-spirit is
called 'over-proof (o.p.) and the weaker one 'under- proof (u.p.)
Significance : Above percentage is considered as the proof-strength of
alcohol and I according to them it is decided whether any liquid is stronger
or weaker.
Examples -
1. Over-proof (O.P.)—
 10° over-proof (o.p) : means that 100 volumes of the liquid
(Alcohol /Spirit) diluted with purified water, will give 110 volumes of
proof-spirit.
 30° over-proof (o.p) : means that 100 volumes of the liquid (Alcohol /
Spirit) diluted with purified water, will give 130 volumes of proof-
spirit.
 60° over-proof (o.p) : means that 100 volumes of the liquid
(Alcohol /Spirit) diluted with purified water, will give 160
volumes of proof spirit.
2. Under-proof (U.P)—
 10° under-proof (u.p) : means that 100 volumes of the liquid contains
90 I (100 - 10) volumes of proof-spirit,
 30° under-proof (u.p) : means that 100 volumes of the liquid contains
701 • (100 - 30) volumes of proof-spirit.
 60° under-proof (u.p) : means that , 100 volumes of the liquid contains
401 | (100 - 60) volumes of proof-spirit.
Determination of proof strength of alcohol :
Proof strength of alcohol means the standard strength of alcohol.
Alcohol freely mixes with water. Almost all the governments of the
world have I imposed some sort of duty on alcohol and I alcohol
preparations. As a result it is necessary to know the strength of alcohol.
Formerly the strength was roughly determined by pouring alcohol
over gun powder and firing it. If the sample contained much water, it did not
take fire and if the quantity was small it took fire easily.
For convenience, a special type of hydrometer has been invented by
the Excise authority to ascertain the strength of alcohol. For this purpose a
mixture containing 1 % by volume of ethyl alcohol and 42.9% by volume of
purified water is called the standard proof-spirit. The strength is measured in
terms of degrees.
The hydrometer is graduated specially, corresponding to the upper
level of the standard proof spirit, above and below of the standard mark
there are equal graduations.
When the strength of an unknown quality of alcohol is to be
determined, the alcohol is taken in a big glass cylinder and the hydrometer is
dipped into it carefully and the upper level of alcohol is read.
If it is seen that the upper level is 60 marks above the standard mark,
expressing its lowered density and, hence, strong due to less amount of
water, it is called 60° o.p.
On the other hand, if the upper level corresponds with a line 20 marks
below the standard mark it is called 20 u.p.
Properties-
 A colourless, transparent, very mobile liquid,
 Sweet smell and burning taste.
 It is very inflammable, boils at 34.5°C and burns with a white flame.
It is extremely volatile.
 Specific gravity : 0.72.
 Solubility - Soluble in 8.5 volumes of water ; miscible in all
proportions with alcohol (90 p.c), Chloroform, fixed and volatile oils.
Most of the alkaloids, resins, balsams, tannic acid etc. are easily
dissolved by it. It dissolves bromine and iodine readily but sparingly
dissolves phosphorus and sulphur. The corrosive sublimate (HgCl2) is
very quickly dissolved by it.
Precautions -
 As solvent ether is highly inflammable and volatile, it should be
always away from the fire and kept tightly corked.
 It should never be used as an anesthetic.

Uses-
 It is used only when alcohol in its varying properties with water
cannot extract the drug substance from plant.
 It is a good solvent for many organic compounds e.g. resins,
gums, fats, oils, cellulose, esters etc.