Assignment Work

Submitted to: Mam Aysha Bukhari

Submitted by: Kainat (25)
Amina Hussain (13)
Neha Tariq (21)
Class: BS Chemistry (7th semester)

Subject: ADVANCE SEPARATION TECHNIQUES

Date: 14-02-2020

MINHAJ UNIVERSITY LAHORE

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Contents

1. Introduction
1.1. Physical state change
1.2. Desublimation
2. Advantages
3. Principle
4. Working
4.1. Simple procedure
4.2. By using sublimation apparatus
5. Examples
6. Applications
7. Limitations
8. Suggestion

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 Topic: Sublimation
1. Introduction:

“Sublimation is the transition from the solid phase to the gas phase without passing through an
intermediate liquid phase”

It is an endothermic phase transition. Sublimation is a purification technique for solids. It is used

for organic compounds with lower melting points.

Elements and compounds mainly possess three different states at various temperatures.

The transition from solid state to gaseous state requires a transition of solid-state to liquid state
and liquid state to a gaseous state.

If solids possess sufficient vapor pressure at a particular temperature then they can directly
sublime into the air.

Solids which have high pressure at their triple point show sublimation.

The triple point is the point at which the pressure and temperature of the substance are such that
it can exist in all three states of matter simultaneously. The triple point is a characteristic point of
a substance.

1.1. Physical state change:

The term "sublimation" only applies to physical changes of state and not to the transformation of
a solid into a gas during a chemical reaction. For example, when candle wax undergoes
combustion, the paraffin is vaporized and reacts with oxygen to produce carbon dioxide and
water. This is not sublimation.

1.2. Desublimation:

The opposite process of sublimation where a gas undergoes a phase change into solid form—is
called deposition or desublimation.

2. Advantages:
o Sublimation is adopted by chemists as a purification technique.
o There are many advantages for performing sublimation over other purification methods.
o This process is principally used for micro scale purifications of solids because the loss of
product is typically very minimal.
o Furthermore, this technique is appropriate for any heat sensitive compound (but under
high vacuum, sublimation can be affected under low temperatures).

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 o Thirdly, unlike recrystallization, solvents are not involved at all in the process, and most
traces of any solvent are effectively eliminated.

However sublimation is only favored over crystallization, when the substance weighs less than
100mg, and has the correct properties. Based on the theory of this phase change, the process is
highly dependent on the different vapor pressures of not only the desired compound, but also on
the vapor pressures of the impurities that are present in the crude.

3. Principle:

Sublimation is a phase transition process from a solid to a gas without ever entering
an intermediate liquid phase. The ability of any types of solids to sublime depends
on the compound’s triple point based on its phase diagram – typically the lower the
pressure, the lower the sublimation temperature. (Note that the pressure and
temperature of the desired substance must be below its triple point in order to
sublime). Solid compounds that can sublime are very rare, for example, solid
carbon dioxide (a.k.a. dry ice) can sublime at 1 atm pressure at 78.5 °C. For
sublimation to occur, a solid must exhibit a higher than usual vapor pressure, i.e. it
must have weak intermolecular attractions. This is normally true for solids with
molecules in the shape of a sphere or a cylinder. The theory for process of
sublimation lies in basic chemical properties. For example, higher temperatures
result in a vapor pressure increase, i.e. the rate of evaporation is increased with
heat. Moreover, a higher rate can be achieved if an evacuated system is used.

Graph of sublimation

4. Working:

There are many ways to conduct sublimation. It can range from a very simple procedure to a
more complicated one.

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 4.1. Simple procedure:

A simple one would include only the use of two Petri dishes, a heat source and a beaker. This
procedure entails having one of the Petri dishes placed on the bottom of the beaker with the
crude material and the second dish situated on top of the beaker. Once the crude is heated, the
sublimate or the purified material will appear on the top dish.

Diagram of sublimation

4.2. By using sublimation apparatus:

Another method requires the use of any of the sublimation apparatus shown below;

Apparatus used for sublimation

This method is carried out but heating the crushed crude solid in a tube or a Buchner flask (both
on top of a heating mantle), while simultaneously evacuating the system. The purified product
will sublime on the cooled condenser – the second inner tube with a water aspirator or on the
tube containing cracked or dry ice) – after sufficient heating is applied under reduced pressure.
Before starting sublimation, it is important to ensure that the apparatus is set up properly – this

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technique is not an easy one and when done improperly, will typically result in major loss of
product.

5. Examples:
o Dry ice is solid carbon dioxide. At room temperature and pressure, it
sublimates into carbon dioxide vapor.
o Freezer burn results from the sublimation of ice into water vapor.

o At the right temperature, the elements iodine and arsenic will sublimate from
solid form into gaseous form.

o Naphthalene, a chemical commonly used in mothballs, readily sublimates at

room temperature and pressure.

o Water ice will sublimate, although more slowly than dry ice. The effect can
be seen over snowfields when the sun is out but the temperatu re is cold.

6. Applications:

1. Sublimation and erosion cause ablation, a process that wears down glaciers.
2. Sublimation of iodine may be used to reveal latent fingerprints on paper.
3. Sublimation is used to purify compounds. It is especially useful for organic compounds.
4. Because dry ice sublimates so readily, the compound is used to produce fog effects.

7. Limitations:
1. The crude material does not sublime: The most common reasons are insufficient heat,
and/or the pressure is not low enough.
2. The sample sublimes, but the material crystallizes on the sides of the filter flask, and
not on the cold finger: The bottom of the flask might be hot enough, but the sides are
not. The material is allowed to sublimate, but cannot reach the cold trap and is able to
crystallize earlier. Insulation of the lower part of the filter flask can be appropriate.
3. I don’t know where the sample went: The crude material was added, but during the
process of heating the flask, the material is gone, and there are no crystals. There can be
several reasons, but the most likely contender is that the cold finger did not efficiently
work as a trap. Lowering the position of the cold finger is a good solution.
4. The crude material is boiling: The system can be too hot, and less energy should be
supplied to heat the system. Potentially the pressure should be reduced.
5. The product crystallizes on the cold finger, but looks pasty and wet and not
crystalline: The ice cold water in the cold finger has been in the finger for too long. The
cold surface has started condensing water from the atmosphere, and once the product
starts to reach the cold surface it is met by water. In general, the ice cold water should be
added to the cold finger right before the sublimation starts to eliminate this problem.

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8. Suggestion:

This technique, which is applicable to many organic solids, can also be used with inorganic
solids such as aluminium chloride, ammonium chloride, arsenious oxide and iodine to name
a few. In some cases, passage of a stream of inert gas over the heated substance secures
adequate vaporisationand reduces oxidation. This procedure has the added advantage of
removing occluded solvent used for recrystallizing the solid.

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References:

https://www.utsc.utoronto.ca/webapps/chemistryonline/production/sublimation.php

https://www.thoughtco.com/definition-of-sublimation-phase-transition-604665

https://chem.libretexts.org/Bookshelves/Organic_Chemistry/Book%3A_How_to_be_a_Successf
ul_Organic_Chemist_(Sandtorv)/02%3A_COMMON_ORGANIC_CHEMISTRY_LABORATO
RY_TECHNIQUES/2.05%3A_SUBLIMATION

https://byjus.com/chemistry/sublimation/

https://www.sciencedirect.com/topics/chemistry/sublimation