Experiment 1:

Melting Point Determination

Introduction

Most crystalline organic compounds have characteristic melting points that are sufficiently low (50-300°C) to
be conveniently determined with simple equipment. Organic chemists routinely use melting points to get an
indication of the purity of crystalline compounds and to help identify such compounds.

The melting point of a pure crystalline substance is a physical constant or property of that substance. A physical
property of a substance is one that is intrinsic to a given substance in its pure form. Pure crystalline compounds
usually have a sharp melting point. That is, the melting point range (the difference between the temperature
at which the sample begins to melt and the temperature at which the sample is completely melted) is small
(narrow). Impurities, even when present in small amounts, usually lower the melting point and broaden the
melting point range. A wide melting point range (more than 5°C) usually indicates that the substance is impure;
a narrow melting point range (0.5-2°C) usually indicates that the substance is fairly pure. However, there are
some exceptions to both of these generalizations. Small differences in melting point (on the order of 2-3°C)
may also result from variations in technique, thermometer accuracy, and the experience of the person doing the
melting point determination.

Melting points can be used in the following way to help identify a compound. Say a sharp melting, unknown
substance X is suspected of being identical to some known substance A. If the two are identical, they should have
the same melting point. Thus, if A is reported in the chemical literature to have a melting point significantly
different from that observed for X, we can be quite certain that X does not have the same structure as A. On the
other hand, if A is reported to have a melting point within a few degrees of that observed for X, the two substances
may be identical (the small difference being due to variations in technique or purity).

To make certain that X and A are identical, one can determine the mixture melting point, that is the melting
point of a mixture of X and A (when a sample of A is available). If X and A are identical, the mixture should have
the same melting point as X or A alone. On the other hand, if X and A are not the same substance (even though
they separately have the same melting point), then a mixture of the two usually has a lower melting point and a
broader melting point range than either substance alone. This is because each substance acts as an impurity in
the other.

To summarize, if a crystalline substance is pure, its melting point range is likely to be narrow. If two samples have
identical structures, their mixture melting point is not depressed, and the melting point range is not broadened.

To determine the melting point of a crystalline substance, we introduce a small amount of the finely powdered
material into a thin-walled capillary tube that is sealed at one end. The capillary tube is inserted into a melting
point apparatus and heated. Three temperatures are recorded:

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 Melting Point Determination

1. the onset point, also called the collapse point, is considered the start of the melt. It is when liquid clearly
appears for the first time as a separate phase in coexistence with the solid crystals.
2. the meniscus point, is when a liquid meniscus becomes clearly visible. There is solid phase at the bottom
and a clear liquid phase on top with a complete and well-defined meniscus.
3. the clear point, is when the substance becomes completely liquid and there is no solid remaining.

The observed melting point range is the interval between these three temperatures. The melting point is a char-
acteristic property of a pure chemical substance.

The observed melting point range can be influenced not only by the purity of the material but also by the size
of the crystals, the amount of material, the density of its packing in the tube, and the rate of heating. A finite
time is required to transfer heat from a hot liquid bath or metal block through the walls of the capillary tube and
throughout the mass of the sample. When the bath or block is heated too quickly, its temperature rises several
degrees during the time required for melting to occur. This can result in an observed range that is higher than
the true one.

When the temperature of the bath or block approaches the melting point of the sample, it is essential for good
results to raise the temperature slowly and at a uniform rate, usually about 2°C/min. The sample should be small,
finely powdered, and packed tightly in a thin-walled capillary tube of small diameter. The column of solid in the
capillary tube should be just high enough to be seen clearly during melting (about 2-3mm).

The behavior of a material upon melting should be observed and recorded carefully. Write, for example, ”Melts
sharply at 89.0—89.5°C” or ”mp 131—133°C, with decomposition” or ”Discolors at 65°C; melts slowly at 67-
69°C”.

The melting point of a sample tells you the purity of that sample and is based upon two factors: melting point
range and melting point depression. Both of these are caused by impurities present in your sample.

In this experiment you will determine the melting points of two different pure solids that have approximately the
same melting point range. You will then prepare a mixture of the two substances and determine its melting point
range. Finally, you will obtain a sample of an unknown from your instructor. After you determine its melting
point, you will identify the substance by finding a mixture melting point.

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 Melting Point Determination

Table 1.1: Melting Point Guide to Purity

Purity Description

Ultra-pure sample Melting point range of 0°C, and melting point

depression 0°C

Very Pure Melting point range of ≤1°C or melting point

depression of ≤1°C

Pure Melting point range of 1°C, and melting point

depression of 1°C

Slightly Impure Melting point range of 2°C, and melting point

depression 1-3°C

Impure Melting point range 3-4°C; or melting point

range 2°C and melting point depression >3°C

Extremely impure Melting point range of >4°C, and/or melting

point depression > 6°C

Procedure

A quickstart guide to the DigiMelt is included at the end of this procedure.

1. Obtain 50-100mg of urea and grind it to a fine power by crushing it with a metal spatula on the surface of a
watch glass.

It is important that the watch glass be completely clean and dry. A wet pulverized sample
will not only yield an erroneous lower melting point range but will also make it difficult
to fill the capillary tube with the required amount of sample for melting point determi-
nation. Melting point samples must be fully dry, homogeneous, and in a fine powdered
form.

2. Fill a melting point capillary tube with a sample of urea by pushing the open end into the powder several
times.

3. To work the solid material down to the sealed end of the capillary tube, gently tap the sealed end on the
bench top.

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 Melting Point Determination

4. Repeat the above steps until the tube contains a 2-3mm column of densely packed powder at the bottom.

For consistent results, it is very important that the capillary is not over or under filled.
Tight packing and a fixed level of sample are very important for optimum results.

5. Insert the tube into the melting point apparatus and start heating.

The temperature may be allowed to rise rapidly to within 10°C below the compound’s ex-
pected melting point. However, during determination of the actual melting point range,
the temperature should not rise more rapidly than 1°C/min. Therefore, decrease the rate
of heating when the temperature is about 10°C below the expected melting point.

6. Determine the melting point range of urea, being sure to record all your observations.

7. In a similar way, determine and record the melting point range of a sample of trans-cinnamic acid.

8. To demonstrate the effect of impurities on the melting point of a pure substance, determine the melting
point range of a 50-50 mixture by weight (use about 50mg of each compound) of urea and cinnamic acid.

9. Repeat the procedure with 75-25 and 25-75 mixtures by weight.

10. Obtain an unknown sample (as assigned by your laboratory instructor). Fill two melting point tubes with
samples of the unknown. Use one tube to determine the approximate melting point and use the second tube
to determine the melting point more precisely, as described below.

11. When the melting point of an unknown substance is to be determined, you can save time if you first obtain
its approximate melting point using a rapid heating rate, say 20°C/min. Then allow the temperature of the
thermometer to drop to 10°C below the approximate melting point. Use a second sample of the substance
to determine the melting point accurately, with a slow heating rate of about 1°C/min.

12. Use the data in the provided table of potential unknown samples to make a preliminary identification of
your unknown sample. Then confirm its identity by using the mixture melting point technique:
Mix about 50 mg of the unknown with an equal weight of the substance you suspect it to be and determine
the mixture melting point. Repeat the procedure, if necessary, to determine with certainty the identity of

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 Melting Point Determination

your unknown sample.

Table 1.2: Table of Potential Unknowns

Compound Melting Point Range (°C)

Acetylsalicylic Acid 138-140

Benzoin 136-137

trans-Cinnamic Acid 132-134

Malic Acid 130-132

Urea 132-134

Waste Management

1. Discard your used melting point tubes in the broken glass box provided in the laboratory room
2. Discard any extra solids into the solid organic waste container located in the waste fume hood.

Before Leaving Lab Checklist

 Record the melting point ranges of urea, trans-cinnamic acid, and the three mixtures of these com-
pounds.
 Record the melting point range of your unknown sample and the process you used to confirm its iden-
tity.

Melting Point Apparatus “DigiMelt” Quick Start Guide

1. Push (Start Temp) and use the (↑ /2) and (↓ /3) buttons to set the starting temperature (at least 5 degrees
below the expected melting point).

2. Push (Ramp Rate) and use the (↑ /2) and (↓ /3) buttons to set the Ramp Rate (1 deg/min is suggested).

3. Push (Stop Temp) and use the (↑ /2) and (↓ /3) buttons to set the Stop Temperature (at least 5 degrees above
the expected melting point).

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 Melting Point Determination

4. Push (Stop Temp) again to return to the current temperature display.

5. Load capillaries with sample. Insert capillaries into the chassis holes near the Tube Tapper button.

6. Press the (Tube Tapper) button to pack your samples.

7. Push (Start/Stop) to preheat the block to the starting temperature. The Preheat LED will light.

8. When the Ready LED becomes lit, the oven is holding at the Start Temperature. Insert your samples into the
DigiMelt oven.

9. Push (Start/Stop) to begin ramping the temperature at the Ramp Rate. The Melt LED will light.

10. Observe your samples during the ramp.

11. Push the (1), (↑ /2) and (↓ /3) buttons to record data (up to 3 temperatures per sample) during the melt. (To
end the experiment before the Stop Temperature is reached, push the (Start/Stop) button.)

12. When the Cooling LED is lit, the experiment is over. If you recorded data, the Data LED is also lit.

13. To read back the data, push the (1), (↑ /2) and (↓ /3) buttons (make sure the Cooling LED is lit).

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Department of Chemistry.