Determining of Melting point and Boiling point

Manalili,Francis kent A. and Samillano,Charlotte Dian P.

Chemistry Department, College of Science
Adamson University
Ermita,Manila

ABSTRACT

The first thing we have done in our experiment. We prepare the things we needed
Before we start the experiment 2 our professor instruct and explain one by one the
methods we need to do. To accomplish the experiment that we need to figure out.
The first thing was the boiling point, We used the 3 capillaries and each of them
contained a reagents like: Acetic acid, Ethanol, and the mix of two chemical.

In the boiling point we used; Oil in and the Thiele-dennis tube supported by the
Iron stand. The capillary is placed in the microtube in an inverted position (with
sealed end uppermost) and the microtube contain the amount of chemicals e.g.
Ethanol, Then the microtubve is attached to the thermometer with a rubber (the tip
of the microtube must aligned with the mercury bulb of the thermometer). The
thermometer and the microtube are supported byt the Tir-prong clamp to secure
that it will not Fall down. We apply heat gradually until a continous stream of
bubbles comes out of the open end of the capillary and passes through the liquid,
then we put off the flame and allow the tube to cool by stirring the oil continuously
with the stirring rod; After that we observe the liquid in the microtube and recorded
the temperature when the bubbles stop coming out of the capillary and just before
the liquid enters it. Then we repeat for another chemicals like:acetic acid and the
Mix.

The second one was the melting point we have done it last Monday, because we did
not finish the experiment last Friday in melting point. First another 3 capillaries
needed we seal one end of each capillary; then we grind it separately in a mortar a
small amount of benzoic acid, urea, and a mix. After we grind it we introduce each
sample gradually into a capillary by pushing the open end of the capillary into the
powder and tapping the closed end on the tbale cloth, the powder should occupy a
height of 1 cm in the capillary. When it already finish we enter the Balance room
and our professor taught us How to use the melting point apparatus; so we already
learn how to operate it. We place the 1 capillary only one at the time then we set
the power switch to the number that correspond to the approximate melting point
of the sample.
1.0 Introduction

Boiling point

The physical properties of a compound, such as melting point and boiling point can
provide useful information which can help in the identification of a sample or to
establish its purity. Since the boiling point of an unknown sample under the same
conditions (e.g. same pressure) is a constant, a measured boiling point can be
compared to known values (e.g. literature value or the measured value of a known
sample). Since this used to be a very important method, there are tables and
collections of boiling point data available and the boiling point is one of the physical
properties of a compound that is commonly recorded and reported (e.g. see
Wikipedia entry for ethanol). If a sample of a liquid is placed in an otherwise empty
space, some of it will vapourise, and the pressure in the space above the liquid will
rise to some constant value. The pressure under these conditions is due entirely to
the vapour of the liquid, and is called the equilibrium vapour pressure. The
phenomenon of vapour pressure is interpreted in terms of molecules of liquid
escaping into the empty space above the liquid. In order for the molecules to
escape from the liquid phase into the vapour phase, the intermolecular forces (in
order of increasing strength: Van der Waals, dipole-dipole, hydrogen bonding) have
to be overcome which requires energy. Since the nature of the intermolecular
forces is determined by the molecular structure, then the amount of energy
required to vapourise the sample also depends on the molecular structure an
example of the relationship between structure and properties. As the number of
molecules in the vapour above the liquid becomes larger, the rate of return of the
molecules from the vapour to the liquid increases until the rate of return is equal to
the rate of escape. This is the equilibrium condition and the corresponding
concentration of molecules in the vapour space gives rise to the equilibrium vapour
pressure At higher temperatures, the greater average kinetic energy of the
molecules in the liquid results in a greater constant rate of escape. Equilibrium is
established at higher temperatures, and so larger numbers of molecules are
present in the vapour phase and the pressure is higher When the vapour pressure
of a liquid is equal to the atmospheric (or applied) pressure then boiling occurs. The
temperature at which this occurs, for a given pressure, is the boiling point.

Micro-Boiling Point Determination (quick link to videos : version 1, version 2)

Before using a Bunsen burner make sure all flammable materials (e.g. solvents) are
removed from the area around the Bunsen burner. This means not only your
workspace but also all the students near to you. When using the Bunsen burner,
make sure that you adjust it to a small flame. If you are unsure of how to set up
and use a Bunsen burner, see the heat sources techniques document and the
video on the Bunsen burner. If only small amounts of liquid material are available
for boiling point determination, then a micro boiling point apparatus based on a
Theile tube should be used. The Thiele tube is a glass tube designed to contain
heating oil and a thermometer to which a micro test tube containing the boiling
point sample is attached. The shape of the Thiele tube allows for formation of
convection currents in the oil when it is heated. These currents maintain a fairly
uniform temperature distribution throughout the oil in the tube. The side arm of the
tube is designed to generate these convection currents and thus transfer the heat
from the flame evenly and rapidly throughout the heating oil. Dont clamp the
Thiele tube too tightly otherwise it might crack as it expands as it is heated, yet of
course it needs to be secure. The sample liquid is introduced by Pasteur pipette into
a micro test tube (no more than 0.5ml, which is about 10mm depth in the small
test tube), and a piece of melting point capillary tubing (sealed at one end) is
dropped in with the open end down. The micro test tube assembly is then attached
to a thermometer with a rubber band or a thin slice of rubber tubing. The whole
unit is then placed in a Thiele tube.

Thiele, is a laboratory glassware designed to contain and heat an oil bath. Such a
setup is commonly used in the determination of the melting point of a substance.
(Fig. 1)

Fig. 1 Thiele setup

The explanation of this method is a reasonably simple one.

During the initial heating, the air trapped in the capillary tube
expands and leaves the tube and vapour from the liquid also
enters the tube. There is always vapour in equilibrium with a
heated liquid. This gives rise to the initial stream of bubbles.
When the temperature reaches the boiling point, the vapour
pressure inside the capillary tube equals the atmospheric
pressure. As the temperature rises just above the boiling
point then the vapour will start to escape : the second set of bubbles. Once the
heating is stopped, the only vapour left in the capillary comes from the heated
liquid which seals its open end. As the liquid cools, its vapour pressure will decrease
and when the vapour pressure drops just below atmospheric pressure, the liquid
will be drawn into the capillary tube (forced there by the higher atmospheric
pressure). Two problems are common to this method. The first arises when the
liquid sample in the micro test tube is heated so strongly that it evaporates or is
boiled away. Once the oil has cooled, add more liquid sample to the small test tube
and resume heating but more gently. The second arises when the liquid is not
heated above its boiling point. If the heating is stopped at any point below the
boiling point of the liquid, the liquid will enter the tube immediately. It will enter the
tube because the trapped vapour will have a pressure less than that of the
atmosphere.

http://www.chem.ucalgary.ca/courses/351/laboratory/boilingpoint.pdf

MELTING POINT

The physical properties of a compound, such as melting point and boiling point
can provide useful information which can help in the identification of a sample or to
establish its purity. These pages describe two common methods for determining
melting point using i a Meltemp apparatus and ii a Thiele tube set up. The
temperature at which a solid melts and becomes a liquid is the melting point. Since
this requires that the intermolecular forces that hold the solid together have to be
overcome, the temperature at which melting occurs will depend on the structure of
the molecule involved - an example of the relationship between structure and
properties. Hence, different compounds tend to have different melting points. A
pure, nonionic, crystalline organic compound usually has a sharp and characteristic
melting C range). A mixture of very small amounts of miscible impurities will
produce apoint (usually 0.5-1.0 depression of the melting point and an increase in
the melting point range. Consequently, the melting point of a compound is a
criterion for purity as well as for identification. The melting point of an organic solid
can be determined by introducing a tiny amount into a small capillary tube,
attaching this to the stem of a thermometer centred in a heating bath, heating the
bath slowly, and observing the temperatures at which melting begins and is
complete. Pure samples usually C; impure samples of the sameC or 189-190have
sharp melting points, for example 149.5-150 C. .C or 186-189compounds melt at
lower temperatures and over a wider range, for example 145-148 It is standard
practice (in order to make the most effective use of time) to carry out a rapid
melting point determination initially (by heating rapidly) to establish an
approximate melting point and then carry out at least two further careful
determinations (by heating more gently, i.e. temperature changing only about
2oC/min) until you obtain two consistent values. The general method is to the heat
the sample indirectly by placing the prepared sample (either packed in a glass
capillary or on a glass cover slip) in or on a heated medium, these days this is most
commonly a heated metal block such as a Mel-Temp apparatus. There are other
designs such as the Fisher-Johns apparatus. A more basic, but just as effective
method is the Thiele tube method where the capillary is immersed in a heated oil
bath. Note that the Thiele tube system is also used for boiling point determination.
IMPORTANT : Note that unlike boiling point, the melting point is relatively
insensitive to pressure and no pressure correction needs to be made.

Packing a capillary for melting point determination Thin-walled capillary melting

point tubes are used to hold melting point samples. This tube needs to be sealed at
one end (pre-sealed tubes should be available in the laboratory, or, an open
capillary can be sealed by inserting the tip into a Bunsen flame near the base of the
flame and turning the tube in your fingers.... ask your TA to show you how to do
this). To pack the tube, the open end is pressed gently into a small amount of the
sample of the crystalline material on a watch glass or weighing paper. To transfer
the crystals from the open end to the bottom of the tube, tap the bottom gently on
the bench top or scratch the top edge of the tube on a small file or a coin with a
milled edge (the video on melting points illustrates how to do this. A densely
packed column of crystals about 3 mm high in the tube is all that is required. A
packed capillary attached to a normal mercury thermometer is shown to the left.
Using a coin with a milled edge to transfer the solid to the bottom of the capillary
tube ORGANIC LABORATORY TECHNIQUES

4 4.3 Mel-Temp Apparatus

A Mel-Temp apparatus equipped with a digital thermometer

is shown above. Note that we have switched to using a
simple digital thermometer inserted into a conductive
metal sleeve in place of a convential mercury or alcohol
thermometer. The diagram on the right shows the
apparatus with the heat shield removed to reveal the inside
structure. The apparatus uses capillary packed samples
(see above). Insert the thermometer into the thermometer
well and the capillary into the channels located on the front
of the thermometer tube (there are slots for three
capillaries). Turn the green LED power switch on (the "1"
position) and turn the black heating control knob in order
to set the power level to obtain the desired heating rate . The sample can be
observed through the lens on the front of the apparatus, the eye should be about
15cm from the lens. Remember that a slow heating rate at the melting point is
needed in order to get an accurate measurement. Record the temperature on the
thermometer when the sample starts to melt and record the temperature again
when all of the sample has melted (this gives you the melting point range). Once
the sample has melted, turn the power to OFF and remove the capillary and dispose
of it in the special container for this purpose. The block will require a little time to
cool - the cooling process can be facilitated by connecting a hose to the in-house
compressed air and blowing the air across the block.

http://www.chem.ucalgary.ca/courses/351/laboratory/meltingpoint.pdf

2.0 Methodology
2.1 Materials and reagents
We used 6 capillaries overall in the experiment, each experiment
contain 3 capillaries. In melting point we used mortar and pestle
(china brand) to grind the 2 reagents: the urea, and benzoic acid.
And for the melting point apparatus (I do not know if it Branded).

For boiling point we used 3 microtube for each experiment to test the
boiling point of the reagents: Acetic acid,and ethanol. Also we used the
thermometer (china brand) to measure the temperature of the liquid
samplel. Then the thiele-dennis tube (china brand) with oil and the
iron stand (china brand) with the tri prong clamp to support the thiele-
dennis tube.

2.2 Instrumentation setup

Melting point apparatus

Briefly, the sample should be dry and ground to a fine powder. Moist and coarse
samples will not give accurate or reproducible melting point determinations. For
efficient heat transfer, ensure the sample is well packed in the bottom of the
tube by tapping on a hard surface. Place the capillary tube in the MEL-TEMP
melting point apparatus. Set the MEL-TEMP at a high enough level like 4 to
make a rapid determination of melting point. Observe the melting process
though the magnifying lens.

Boiling point

First the micro test tube should be on the same side of the Thiele tube as the
elbow,neither the test tube nor the thermometer bulb should be touching the glass
walls of the Thiele tube.the base of the micro test tube should be just below the
joint to the upper part of the elbow then the rubber band should be placed well
above the level of the oil in the Thiele tube, and,the oil level should be just above
the top of the top elbow joint. If the rubber band enters the oil, the band may
soften and break in the hot oil allowing the micro test tube to fall into the oil. When
positioning the band, one should bear in mind that the oil will expand when it is
heated. Once the set up has been complete, the lower part of the side arm of the
Thiele tube is carefully heated with a small flame from the Bunsen burner moving
the flame back and forth along the arm. During the heating, there is an initial
stream of bubbles as air is expelled and then, a little later, a rapid and continuous
stream of bubbles emerges from the inverted capillary tube. At this point stop
heating. Soon the stream of bubbles will slow down and stop. When they stop, the
liquid sample will be drawn up in to the capillary tube. The moment when the liquid
enters the capillary corresponds to the boiling point of the liquid,and the
temperature should be recorded.