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2+melting Point+Analysis

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2+melting Point+Analysis

Uploaded by

Jaznemileth Grillo
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© © All Rights Reserved
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24

Place the melting-point capillary tube in a cooled heat source and, for an unknown, determine an
approximate melting-point range by raising the temperature rapidly and recording the value at which the
sample melts. Prepare a fresh sample, allow the apparatus to cool somewhat and carry out a second, more
accurate melting-point determination. This time, for an unknown, or the first time for a known, raise the
temperature rapidly until it is within 10–20 oC of the approximate or known value, and then lower the rate
of heating to 2–3 oC per minute. Maintain this heating rate to the end of the trial. The melting-point
range begins at the temperature at which the solid first begins to melt and ends at the
temperature at which it becomes entirely liquid. Always observe and record the melting-point range,
from the temperature of first melting to the temperature of complete liquefaction.

Mixed Melting Points

It often is useful to run a mixed melting-point determination to identify an unknown compound.


If a pure unknown x is suspected of being a known compound y, a melting-point determination should be
run on a mixture of x with a small amount of y. If x and y are identical, the mixture will melt sharply at the
same temperature as pure x. If x and y are different, the mixture usually will melt over a wide temperature
range, and will begin to melt at a temperature lower than the melting point of either pure x or pure y.4

If a eutectic mixture of x and y was formed, the melting-point range will be sharp, but the melting
temperature usually will be lower than either pure x or pure y. (Refer to Figure 2. Note that the eutectic
temperature, TE, is lower than either B or F.) If you suspect that you prepared a eutectic mixture, simply
add more of one component to form a non-eutectic composition. Then observe the melting-point range of
this modified mixture.

Experimental

Safety

Adipic acid, benzoic acid, o-chlorobenzoic acid, trans-cinnamic acid, 4'-hydroxyacetophenone,


2-naphthol, and urea are irritants.
Acetanilide and salicylic acid are toxic and are irritants.
All flammable materials must be kept away from microburner flames.
Mel-Temp machines can be very hot when in use.
Handle thermometers carefully. Report broken thermometers to the instructor,
so that proper clean-up of any spilled mercury can be done immediately.
25
Procedure

1. Evaluation of Purity by Melting-Point Determination

Use a Mel-Temp apparatus and follow the procedure described above to determine the melting-
point ranges of pure urea, pure trans-cinnamic acid, and a 50:50 mixture of the two compounds.

2. Melting-Point Determination of an Unknown

The purpose of this experiment is to carry out the partial identification of an organic compound by
means of mixed melting-point determinations. Obtain an unknown from the instructor. Then introduce a
small amount of the sample into a melting-point capillary tube.

Use a Mel-Temp apparatus to heat the filled melting-point capillary tube rapidly to obtain an
approximate melting-point reading. Then cool the heat source and obtain a more accurate reading by
warming a second filled capillary tube rapidly to 10–20 oC below the approximate melting point, and then
slowly at a rate of not more than 2–3 oC per minute. Observe and record the melting-point range, from the
time the sample first begins to melt until it becomes entirely liquid.

When you are confident that you have obtained an accurate value for your unknown, compare it to
the melting-point ranges of the compounds listed in Table I, below. Select three compounds whose
melting-point ranges agree most closely with your unknown and obtain a small sample of each. (Take very
little; 2–3 mg will suffice!)

Table I: Possible Unknowns and Literature Melting-Point Ranges

compound melting-point range (oC) compound melting-point range (oC)


acetanilide 113–115 trans-cinnamic acid 133–134
adipic acid 152–154 (+)-glucose 153–156
benzamide 128–129 4'-hydroxyacetophenone 109–111
benzanilide 162–164 (+)-mandelic acid 120–122
benzoic acid 122–123 2-naphthol 122–123
benzoin 135–137 salicylic acid 158–160
o-chlorobenzoic acid 138–140 urea 134–136
26
Make 50:50 mixtures of each of the chosen standards with your unknown by thoroughly grinding
together equal amounts of the two compounds. Determine the melting-point ranges of each of these three
mixtures. The Mel-Temp instruments have spaces for three melting-point capillary tubes. Therefore, the
three melting-point ranges can be observed simultaneously. (Just be careful to label the capillary tubes, and
not mix them up!)

For further clarification, it is helpful to run melting-point determinations on the pure and the mixed
samples simultaneously, so that their melting behaviors can be compared directly. To do so, place your
unknown in capillary tube #1, the 50:50 mixture of your unknown and a standard in capillary tube #2, and
the standard in capillary tube #3. Observe the three melting-point ranges simultaneously.

If a mixture exhibits a melting-point range which is much lower and broader (12–15 oC wide) than
that of the original unknown sample, then the two compounds are not the same. If the melting-point
range of a mixture is similar to that of the original unknown, then the two compounds are the same (unless
a eutectic mixture was formed) and you have identified the compound. On the basis of the mixed melting-
point determinations, decide which of the compounds is your unknown. Report the melting-point range of
your unknown and its identity.

Notes

1 In order to affect the melting-point range of a solid substance, the impurity must be at least
somewhat soluble in the liquid melt. In practice, this condition is almost always met.

2 The extension of the liquid curve, BD, shows the vapor pressure of supercooled liquid x at
temperatures from TB to TD. The line BD is dotted because it is a metastable condition which
can exist only in the absence of any solid phase. If solid x is added to the supercooled liquid,
immediate crystallization of part of liquid x occurs and the heat of crystallization raises the
temperature to TB, where solid and liquid phases can exist in equilibrium.

3 The system is understood to be one in which the components are completely miscible in the
liquid phase and the solid phases consist of pure components.

4 This is not necessarily true when solid x and solid y are soluble in each other. Fortunately,
this theoretically more complicated case is not encountered in organic chemistry very often.
27
Questions

1. What effect would each of the following have on a sample's observed melting-point range?
(a) Use of a thick-walled melting point tube.
(b) Rapid heating.
(c) Use of so much sample that the filled portion of the capillary tube extends considerably
beyond the thermometer bulb.
(d) Poor circulation of the heating bath liquid.

2. Melting-point ranges ordinarily are determined in glass apparatus. This means that glass
constitutes an impurity in the system. Why does the glass have no noticeable effect on the
melting-point ranges?

3. A student suspected that an unknown was undergoing a chemical change at its melting point.
Suggest a simple method for testing the hypothesis.

4. Why does a soluble impurity reduce the melting-point range of a pure compound?

5. Why is it advisable to run a mixed melting-point determination on samples of two different


compositions before concluding that the two compounds are identical?
28
Report Name: ________________________
Unknown Date: _________________________
Instructor: _____________________

REPORT FORM: MELTING-POINT ANALYSIS

Evaluation of Purity by Melting-Point Determination

Pure urea: _________ oC


Pure trans-cinnamic acid: _________ oC
50:50 Mixture of urea - trans-cinnamic acid: _________ oC

Melting-Point Determination of an Unknown

Unknown number: _________


Observed melting-point range: _________ oC

Possible standards: _________________


_________________
_________________

Unknown mixed with: _________________ gave melting-point range: _________ oC


Unknown mixed with: _________________ gave melting-point range: _________ oC
Unknown mixed with: _________________ gave melting-point range: _________ oC

Identity of unknown: _____________________

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