DIGITAL ASSIGNMENT 2

Naman Gupta

15BCM0031

Q1. Explain the various distillation techniques. 


Distillation is a process involving the change of a fluid into vapor that is in this way
consolidated back to fluid structure. It is exemplified at its most straightforward when
steam from a pot gets to be stored as drops of refined water on a frosty surface.
Distillation is utilized to separate fluids from nonvolatile solids, as in the partition of
alcoholic mixers from fermented materials, or in the separation of two or more fluids
having distinctive boiling points, as in the separation of gasoline, kerosene, and
lubricating oil from crude oil.

SIMPLE DISTILLATION
 Requires the utilization of a still or retort in which a fluid is heated, a
condenser to cool the vapor, and a collector to gather the distillate.
 In heating a blend of substances, the most unstable or the least boiling distils
to start with, and the others accordingly or not under any condition.
 This straightforward mechanical assembly is totally acceptable for the purging
of a fluid containing nonvolatile material and is reasonably adequate for
isolating fluids of different boiling points (ATLEAST 70"C)
FRACTIONAL DISTILLATION
 Used to separate liquids whose boiling point lies close to each other i.e.
which cannot be separated by Simple Distillation.
 In this operation the vapors from distillation are over and over
condensed and revaporized in a insulated vertical segment. Particularly
imperative in this association are the still heads, fractionating columns,
and condensers that allow the arrival of a portion of the consolidated
vapor toward the still.
 The goal is to accomplish the nearest conceivable contact between
rising vapor and plunging fluid in order to permit just the most volatile
material to continue as vapor to the beneficiary while giving back the
less volatile material as fluid toward the still.
STEAM DISTILLATION
 Like vacuum distillation, steam distillation is a strategy for refining mixes
which are delicate to heat.
 The temperature of the steam is easier to control than the surface of a
heatingcomponent, and permits a high rate of heat exchange without heating at
a high temperature.
 This procedure includes percolating steam through a warmed blend of the
crude material. By Raoult's law, a portion of the target compound will
 vaporize (as per its partial pressure). The vapor blend is cooled and condensed,
normally yielding a layer of oil and a layer of water.
 Steam distillation of various aromatic herbs and flowers can result in two
products; an essential oil as well as a watery herbal distillate. The essential oils
are often used in perfumery and aromatherapy while the watery distillates
have many applications in aromatherapy, food processing and skin care.

VACUUM DISTILLATION
 Vacuum distillation is a special method of separating compounds at pressure
lower than the standard atmospheric pressure.
 Under this condition, the compounds boil below their normal boiling
temperature.
 Hence, vacuum distillation is best suited for separation of compounds with
higher boiling points (more than 392°F), which tend to decompose at their
boiling temperature.
 Vacuum distillation can be conducted without heating the mixture, as is
usually followed in other distillation types.
 For the separation of some aromatic compounds, vacuum distillation is used
along with steam distillation. When vacuum distillation is combined with
fractional distillation method, components of a mixture get separated very
easily.
ZONE DISTILLATION
 Zone distillation is a distillation process in long container with partial melting
of refined matter in moving liquid zone and condensation of vapor in the solid
phase at condensate pulling in cold area.
 The process is worked in theory. When zone heater is moving from the top to
the bottom of the container then solid condensate with irregular impurity
distribution is forming. Then most pure part of the condensate may be
extracted as product.
 The process may be iterated many times by moving (without turnover) the
received condensate to the bottom part of the container on the place of refined
matter.

Q2. Enumerate on the industrial preparation of mono sulfonated naphthalene.

Ans2.
The sulfonated product are made my direct sulfonation of napthlene with acid or
oleum.
The mechanism is Electrophilic Aromatic Substitution:
Always a mixture of product is obtained. We can achieve the desired isomers by:
varying hydrocarbon ratio, acid concentration and time-temperature relationship. No
sulphonic group can be introduced ortho, para to an existing group.
On disulfonation of napthlene-mono-sulphonic acid, we get sulphonic group on the
unsulfonated ring.

PROCEDURE
 The hydrocarbon is reacted with sulfuric acid; in addition to the
desired isomer, about 15% of the alpha isomer is additionally formed.

 Naphthalene (3,350 1b - 26.2 1b moles) is charged to a cast iron

sulfonation pot, 500 gallons limit, furnished with propeller or anchor
agitator and warmed either specifically with generator gas or by high-
weight (100 1b) pressure steam. It is liquefied by warming to 90-110
°C.

 Sulfuric acid (3,350 lb of 96% strength - 32.8 lb moles) is then

included with agitation (unsettling), the temperature being permitted to
ascend to around 160 °C. The batch is held at 160 - 165°C for about
2hrs to finish response, amid which time water (approx. 400 lb-22.2 lb
moles) and naphthalene (approx. 350 lb - 2.7 lb moles) distil off and
are gathered by condensation.

 The reaction product contains for the most part monosulfonic acids (85
% beta and 15% alphas) in addition to a few sulfone,free sulfuric acid,
disulfonic acids and tar. The undesired α-sulfonate is evacuated by
 blowing dry steam into the charge to impact hydrolytic desulfonation,
the liberated naphthalene being distilled and recuperated. It is vital to
utilize dry steam to stay away from frothing and to keep up a
temperature in the range 160-165°C to guarantee rapid reaction.

 Around 16% or 540 lb of the original naphthalene utilized is

recuperated, leaving the β-sulfonate tainted with just around 0.1%
alpha isomer.

 The hydrolyzed sulfonation blend is released into the water with great
agitation. Also, the subsequent solution is kept running into the saline
solution to form the sodium sulfonate salt. The slurry so obtained is
agitated for 10 hr as it cooled to 30 °C this yields an effortlessly
filterable precipitate.

 The filtration is refined by pumping or blowing the sodium sulfonate

suspension into a weight filter containing wooden plate channels and
elastic covered casings.

 The shell of the filter is covered with tar to minimize corrosion. The
filtrate is license to stand and more salt is included if necessary and
afterward it is refiltered to gather any extra sulfonate that has solidified
out.

 The second yield of sodium sulfonate is not as pure as the first. The
filter cakes are washed with at least water and these washings are
utilized to advantage as a major aspect of the liquor in the sulfonation
dilution tank. The filter cake of sodium sulfonate containing about

 70 % water is squeezed powerfully to a water substance of around

30%. The press cakes are dried to moisture substance of around 5%,
crumbled and conveyed to the caustic fusion pots for transformation to
β - naphthol.
  The yield is around 90% of hypothesis on the premise of naphthalene
consumed.

Factors which ensure rapid and complete sulfonation are :-

1. Use of about 25% excess acid, corresponding to about 40% excess
over that actually converted to sulfonate
2. Distillation of a quantity of water (22.2 moles) only slightly less than
the amount of naphthalene (23.5 moles) sulfonated
3. Use of an elevated reaction temperature. At this temperature, water
will distill from dilute acid until it has increased to 68% in
concentration, which is above the concentration (64%) required to
sulfonate naphthalene at this temperature.

Q8. Give a note on craig method and recrystallization of solid products.

CRAIG’s METHOD

Theory

A method of multiple liquid-liquid extractions is countercurrent extraction, which

permits the separation of substances with different distribution coefficients (ratios). A
clever design known as Craig apparatus is used for this purpose (Lyman C. Craig,
1943).

Craig apparatus consists of a series of glass tubes (r: 0, 1, 2..) that are designed and
arranged such that the lighter liquid phase is transferred from one tube to the next.
The liquid-liquid extractions are taking place simultaneously in all tubes of the
apparatus which is usually driven electromechanically. In the following animated
picture of a single glass tube the typical "extraction/transfer" cycle is shown.
The lower (heavier) phase of the two-phase solvent system (e.g. water, blue layer in
the picture) is the "stationary phase", whereas the upper (lighter) phase (e.g. hexane,
red layer in the picture) is the "mobile phase".

In the beginning, tube #0 contains the mixture of substances to be separated in the

heavier solvent and all the other tubes contain equal volumes of the same solvent. The
lighter solvent is added to tube #0, extraction (equilibration) takes place and the
phases are allowed to separate. The upper phase of tube #0 is then transferred to tube
#1 and fresh solvent is added to tube #0, and the phases are equilibrated again. The
upper layers of tubes #0 and #1 are simultaneously transferred to tubes #1 and #2
respectively. This cycle is repeated to carry on the process through the other tubes of
the apparatus. Obviously, substances with higher distribution ratio move faster than
those with a lower distribution ratio.

It is interesting to examine the distribution of a substance A in each tube after a given

number of equilibration/transfer cycles.

Supposing that the volumes of each solvent are equal (V), and let W represent the
weight of A in the sample, p and q represent the fraction of A with distribution ratio
of D in the upper (organic solvent, o) and lower (water, w) phase, then it is

Since p+q = 1, we have

The fractions of solute in successive tubes after each extraction step are shown in the
following figure:

We observe that after n transfers/equilibration cycles, and since the ratio D=p/q must
be maintained for each tube after the equilibration step, the total fraction of A in each
tube corresponds to the terms of the binomial expansion (p+q)n. Therefore the total
fraction of solute in tube r after n transfers is given by (remember that 0!=1).

By combining with the previous expressions of p and q we finally obtain

The greater the difference of the distribution ratio of various substances, the better the
separation between each other. A much larger number of tubes is required to separate
mixtures of substances with almost similar distribution ratios.
DISADVANTAGES

The Craig apparatus is only rarely used because modern chromatographic techniques
are by far more efficient and convenient. However countercurrent extraction is
educationally very useful since it introduces the student to the fundamental concept of
equilibration between mobile and static phases. Each tube where a complete
equilibration takes place corresponds to one theoretical plate of the chromatographic
column. Craig apparatuses with more than about 100 tubes are very difficult are very
difficult to construct and operate, and they must be compared with modern
chromatographic columns that may exhibit efficiencies of tens of thousands
theoretical plates.

APPLICATION

• Particularly for biological molecules such as

peptides, hormones and other natural
products.
RECRYSTALLIZATION OF SOLIDS

Recrystallization of solids is an important procedure to master since it is one of the

techniques utilized regularly for purification of solids. Other techniques for purifying
solids incorporate sublimation, extraction and chromatography. In any case,
notwithstanding when one of these alternative methods of purification has been
utilized, the solid material thus isolated may at present be recrystallized to accomplish
the most elevated conceivable condition of purity.

The procedure of recrystallization includes disintegration of the solid in a proper

solvent at an elevated temperature and the resulting re-arrangement of the crystals
after cooling, so that any contaminations stay in solution. This system, called solution
re crystallization, is talked about here. An optional approach includes dissolving the
solid without solvent and after that permitting the crystals to re-shape so that the
impurities are left in the melt. This strategy is rarely utilized as a part of the organic
lab in light of the fact that the crystals regularly shape out of a viscous oil that
contains the impurities and from which it is hard to isolate the sought pure solid. It is
fascinating to note, in any case, this is the procedure used to set up the high-virtue
single crystals of silicon utilized as a part of PC chips.

All solids are more dissolvable in a hot than in a cold solvent, and solution
crystallization exploits this reality. In this manner, if a solid is initially broken down
in a measure of hot solvent inadequate to break down it when cold, crystals ought to
shape when the hot solution is permitted to cool. The degree of precipitation of the
solid relies upon the distinction in its solubility in the specific solvent at temperatures
between the extremes utilized. The upper extreme is controlled by the boiling point of
the solvent, though as far as possible is generally directed by exploratory
accommodation. For instance, an ice-water bath is regularly used to cool the solution
to 0 °C, though ice-salt and Dry Ice-acetone baths are ordinarily used to cool solutions
to - 20 °C and - 78 °C, respectively. The solid ought to be recuperated with more
prominent proficiency at these temperatures, provided the solvent itself does not
solidify.

On the off chance that the impurities present in the first solid blend have broken down
and stay disintegrated after the arrangement is cooled, disengagement of the crystals
that have formed ought to in a perfect condition to give pure material. On the other
hand, the impurities may not break up at all in the hot solution and might be expelled
by filtration before the solution is cooled. The crystals that along these lines structure
ought to be purer than the first solid mixture. Arrangement recrystallization is rarely
so basic by and by, yet these two glorified speculations do plot the fundamental
standards of the system.