Chem 118B Organic Health Sciences III:
Lab E - Melting Point Determination
Purpose
The purpose of this experiment is to accurately measure the melting points of both pure compounds and a mixture
of two compounds, and to examine how the melting point is affected by the composition of the mixture.
Learning Objectives
Set up and measure microscale melting points.
Determine if a substance is pure or a mixture by comparing melting points.
Understand the chemical principles behind colligative properties and eutectic points.
Equipment Chemicals
Melting point point apparatus DL-Mandelic acid DL-mandelic acid
capillary tube Spatula trans-Cinnamic acid and trans-cinnamic
EZ-Melt melting Weigh paper Mixtures of acid
References –
Pavia, D. L.; Lampman, G. M.; Kriz, G. S.; Engel, R. G.; Introduction to Laboratory Techniques: A Microscale Ap-
proach, 4th Ed., Brooks-Cole, 2007, pg 627–637.
Theory and Background
Introduction
Melting points are physical constants. The exact temperature where a substance converts from solid to liquid is
used as an identifying characteristic of the compound and can be used to match an unknown compound to a
known substance or as part of the description of a new compound. Some compounds do not have easily mea-
surable melting points, but the majority of common organic solids will have a measurable transition between
solid/liquid. Compounds that do not have melting points include substances that sublime (convert to a gas rather
than liquid), and some substances that react with air (e.g., O2 , CO2 , or H2 O), contaminants, or themselves at high
temperatures, resulting in decomposition/reaction prior to melting.
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Lab E - Melting Point Determination
Pure substances
A sample is made by pressing the open end of a capillary tube into a small amount of solid crystals. The tube
can then be inverted, and the closed end gently tapped on the bench-top to drive the crystals to the bottom of the
capillary (0.5 cm of packed solid at the bottom of the tube is typically sufficient). The capillary tube is heated
gently and the solid is observed carefully. If the approximate melting point is known the sample can be heated
quickly to 10–15 °C below the known melting point, then the heating should be slowed to < 2 °C per minute.
Modern automated melting point apparatus can be programmed to heat at a particular profile and record the
melting range by analysis of a digital image.
The temperature range from where the crystals first begin to soften and blend together (fuse) until all the visible
crystals are gone is the melting point. If the substance is held exactly at the melting point, an equilibrium exists
between molecules in the solid form and the liquid form, and the material will exist in both phases until the
temperature is raised higher than the melting point. The melting point of a pure substance is typically a small
range of 1–2 °C. If a larger range is seen for a pure substance it is possible the sample was heated too quickly and
the surrounding heat source warmed faster than the sample causing an error. The sample should be repeated
with a slower rate of heating.
Mixtures
The presence of impurities will significantly affect the melting point of a substance. Even in the presence of im-
purities solids tend to crystallize mostly as pure substances, this leaves small crystals or inclusions in the crystals
containing the impurities. As the sample begins to melt these impurities produce a solution with the major sub-
stance as solvent and the impurities as solute. It is simple for a molecule of solid to separate from the crystal and
enter the liquid solution if the energy is high enough, but as the energy lowers it is entropically unfavorable for
the molecule to leave the solution and return to the pure solid. This skews the equilibrium causing melting point
depression.
Melting point depression is a colligative property of solutions that lowers and broadens the range of temperatures
range of the melting point. Increasing the number (not type or properties) of solute particles/impurities will have
an increasing effect on the melting point. The minimum/broadest melting point occurs at the eutectic point where
the moles solute equal the moles solvent and the entropy of the solution is at a maximum. Past that point the
solute becomes the solvent and the melting point range increases up to the melting point of the pure solute.
Chemists use mixed melting points in a variety of ways to help identify compounds. If a recrystallized sample
has a sharp (1–2 °C range) melting point it can be expected to have a high degree of purity. So sharp melting
points that match the literature value of a substance can be used as a measure of purity of a known compound.
However, many organic substances have similar melting points. If a known sample is available a chemist may
confirm the identity of an unknown by intentionally mixing two substances. Three samples are made (known
Laboratory Manual Prepared by Catalyst Education, LLC for the University of California at Davis E.2
Department of Chemistry.
Lab E - Melting Point Determination
substance A, unknown substance B and mixed A + B) and the melting points are measured simultaneously to
minimize any error caused by different heating. If all three show similar melting profiles then A = B and the
identity of the unknown is determined. If the mixed sample shows a different melting profile then A ≠ B and
while the identity of the unknown isn’t determined, it can be confirmed that it’s not compound A.
Important Considerations for Melting Points
• If your sample isn’t dry, attempting a melting range determination is a waste of time—your results
will be meaningless!
• Only put 2–3 mm of your sample into the capillary tube—more than that can cause erratic results.
Bubbles that interfere with the ability of the camera to accurately determine the beginning and end of
melting are more likely to form in an overloaded capillary tube.
• Be sure to wipe off the outside of the capillary tube with a Kimwipe® to avoid having powder burn on
the inside of the heating block.
• A ramp rate of 1 °C/min is ideal; 2 °C/min is acceptable; any higher rate will result in an inaccurate range
determination—the range will be shifted and broadened. The higher ramp rates (up to 20 °C/min) are
useful when you have no idea of the melting range of your sample. This situation arises when you have
made a derivative of an aldehyde or ketone unknown. In this case, you would set a broad range and a
rapid ramp rate to get an approximate idea of the melting range. Then, using a freshly loaded capillary
tube, set a narrower range and a slower ramp rate for an accurate determination.
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Lab E - Melting Point Determination
Procedure
Safety Precautions
• Dispose of used capillary tubes in the glass disposal box. NOT THE TRASH!!
• This experiment will be done as a group.
Making A Sample
1. Make a small pile of DRY crystals on a weigh paper or in a vial. If the crystals are large break them up with a
spatula to a powder so they fit in the capillary tube. Damp crystals will give poor melting points, make sure
the crystals are dried.
2. Gently press the open end of the capillary tube into the pile of crystals so small amounts of solid are pressed
into the tube.
3. Turn the tube so the open end is up and gently tap the closed end on the bench to shake the crystals down
to the bottom of the capillary tube. Your TA will demonstrate the technique.
4. Repeat until you have approximately 2–3 mm of packed solid at the bottom of the capillary tube. Do not
overfill the capillary tube. Extra sample will cause problems with the automated melting point apparatus.
5. Clean the outside of the capillary tube with a Kimwipe® to remove any extra solid or contaminants. Materials
on the outside of the tube will cause errors and contaminate the melting point apparatus.
6. Do not insert sample until instructed.
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Lab E - Melting Point Determination
Setting up the EZ-Melt
7. Adjust the Start Temperature: Press the yellow “SET” button once to display the Start Temperature. Adjust
the Start Temperature by pressing the START/RAISE button or the STOP/LOWER button. The Start Temper-
ature should be set to ~5–10 degrees below the expected melting point. Pressing and holding either button
will change the setting by greater amounts.
8. Choose a Ramp Rate: The Ramp Rate is the fixed rate of temperature rise between the Start and Stop Tem-
peratures. The Ramp Rate is the most important instrument parameter affecting the accuracy and
reproducibility of measurement of melting points. A Ramp Rate of 1 degree/min is appropriate for
most routine determinations. Press the yellow “SET” button again to display the Ramp Rate. Adjust the
Ramp Rate by pressing the START/RAISE button or the STOP/LOWER button.
9. Adjust the Stop Temperature: Press the yellow “SET” button again to display the Stop Temperature. Adjust the
Stop Temperature by pressing the START/RAISE button or the STOP/LOWER button. Pressing and holding
either button will change the setting by greater amounts. The Stop Temperature should be set ~5–10 degrees
higher than the expected melting point.
10. Finish setup: Press the yellow “SET” button again to finish setup. The yellow “SETUP” LED turns off and
the display returns to the current oven temperature.
11. Preheat the oven to the Start Temperature: Press the green “START” to preheat the oven to the Start Temper-
ature. An audible tone is heard and the “INSERT SAMPLES” LED is turned on when the oven stabilizes at
the Start Temperature.
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Lab E - Melting Point Determination
Running the Melting Point
12. Insert the sample capillary: Insert the clean capillary sample tube(s) into the oven via the ceramic insulator
on top of the unit and wait a few seconds for the temperature of the oven to stabilize. NEVER FORCE A
CAPILLARY INTO THE HEATING BLOCK! Once the capillary is inserted into the sample hole, it should
literally drop down to the bottom of the heating stand.
13. Initiate the heating ramp: Press the green “START” button again to initiate the temperature ramp and the
automated melt determination process. The “MELTING” LED is on indicating that the oven is ramping from
the Start to the Stop Temperature. The capillary tubes must not be disturbed while this ramping takes
place.
14. View the melt: During the heating ramp, EZ-Melt will make an automatic determination of the onset point
and clear point for each capillary present. Manual determinations may be recorded during the melt as well.
15. Finish the ramp: The heating ramp is terminated when the Stop Temperature is reached, or press the red
“Stop” button to terminate the ramp early (if you observe that the melting process is complete). The oven
will cool back down to the Start Temperature in preparation for another determination. If EZ-Melt was able
to make an automatic melting point determination, the “DATA” LED will flash indicating that the melting
temperature data is available and needs to be read.
16. Recall the information: When the “DATA” LED is flashing, there is new melting point data which needs to
be read before starting the next measurement. Once the next measurement is started, the stored data is
erased! Press one of the “SAMPLE” buttons to see the results for that sample. The LED in the “SAMPLE”
button lights indicating which sample’s data is being displayed. Each press of the button shows the next
recorded temperature in the following sequence-Auto 1 (onset of melting), Auto 2 (clear/end of melting),
Manual 1, 2, 3, & 4 (recorded by pressing the proper “SAMPLE” button during the melting process-see ex-
panded instructions). The “AUTO” LED is on when one of the automatic determinations is displayed. A
“_” in the display indicates that there is no data for that entry in the sequence. No automated results are
displayed for sample slots that do not contain capillaries or for samples that did not melt during the analysis.
Repeat this procedure for all the samples analyzed. Once the results are read, the “DATA” LED will turn off.
17. Prepare for the next melt: EZ-Melt automatically cools down to the Start Temperature at the end of a melt.
When the oven stabilizes at the Start Temperature again, the audible tone is sounded and the “INSERT
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Lab E - Melting Point Determination
SAMPLES” LED turns on. Return to Step 7 to perform another melt at the same temperature or return to S
tep 2 to program a new set of temperatures.
18. Turn the oven off : Press the “STOP” button to turn off the oven. The “OPERATE” LED will turn off indi-
cating that the oven is cooling off to ambient. If the unit is in the middle of a ramp, pressing the “STOP”
button terminates the ramp and the oven will return to the Start Temperature. In this case, press the “STOP”
button again until the “OPERATE” LED turns off. The oven will also turn off automatically after holding
the Start Temperature for 30 minutes with no user input.
Making a Melting Point Curve.
19. Following the protocol listed in steps 1–6 make up a melting point capillary with 100% DL-mandelic acid.
20. Following the protocol listed in steps 1–6 make up a melting point capillary 100% trans-cinnamic acid.
21. Following the protocol listed in steps 1–6 make up a melting point capillary with one of the provided mixed
samples:
Table E.1: Mixed Sample Assignments
Locker # Assigned Compounds and Mixtures
1, 7, 13, 19 80% trans-cinnamic acid : 20% DL-mandelic acid
2, 8, 14, 20 65% trans-cinnamic acid : 35% DL-mandelic acid.
3, 9, 15, 21 50 % trans-cinnamic acid : 50 % DL-mandelic acid.
4, 10, 16, 22 40 % trans-cinnamic acid : 60 % DL-mandelic acid.
5, 11, 17, 23 30 % trans-cinnamic acid : 70 % DL-mandelic acid.
6, 12, 18, 24 20 % trans-cinnamic acid : 80 % DL-mandelic acid.
22. Following the protocol listed in steps 7–18 run melting points of all three samples simultaneously.
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Lab E - Melting Point Determination
23. With the help of your classmates make a table of melting points for all 8 samples and record the data on your
report sheet.
24. Include a plot of data with your lab report.
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Name:
Report Sheet:
Section: Date: Lab E - Melting Point Determination
Lab Day: M T W Th
+ Locker #: TA:
Lab Time: 9:00 am 1:10 pm 4:10 pm 7:10 pm
Data Collection
Individual Data
Report Table E.1: Melting Point Data
Sample % Composition Melting Point Range (°C)
DL-mandelic acid 100%
trans-cinnamic acid 100 %
assigned mixture
Group Data
Report Table E.2: Group Melting Point Data
Sample Sample 1 (°C) Sample 2 (°C)
80% trans-cinnamic acid : 20% DL-mandelic acid
65% trans-cinnamic acid : 35% DL-mandelic acid
50% trans-cinnamic acid : 50% DL-mandelic acid
40% trans-cinnamic acid : 60% DL-mandelic acid
30% trans-cinnamic acid : 70% DL-mandelic acid
20% trans-cinnamic acid : 80% DL-mandelic acid
Laboratory Manual Prepared by Catalyst Education, LLC for the University of California at Davis E.1
Department of Chemistry.
Lab E - Melting Point Determination Report Sheet
Comments
Describe any special conditions, errors, or deviations from the stated procedure below:
Questions
1. Describe the process of melting in your own words.
2. How does an impurity affect the melting point?
3. Substance A has a melting point of 80 °C and substance B has a melting point of 69 °C. If you start with
pure A and add larger percentages of B what would happen to the melting point at 0% B, at 10% B, at
50% B, at 90% B at 100% B. (Describe the general process, you don’t need to give exact melting points.)
Laboratory Manual Prepared by Catalyst Education, LLC for the University of California at Davis E.2
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Lab E - Melting Point Determination Report Sheet
4. If you mix two substances when would you expect to get the lowest melting point? (Circle correct
answer).
a. When mass is equal
b. When mols are equal
c. Other
5. Plot mp vs. % on the graph below with appropriate axis labels.
6. What mixed concentration measured gives the lowest mp and why?
7. Melting point samples need to be dry to give accurate data. Why does solvent affect the melting point?
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