Organic Chemistry Lab

Experiment #2 Melting Point

Purpose
The purpose of this laboratory session is to learn how to accurately determine the
melting range of a solid substance, to observe the effect of the purity of a
substance on its melting behavior, and to use a physical constant of an unknown
its melting point to identify it from among several possible compounds.

Outcomes
As a result of todays laboratory you will have:


1. packed a capillary tube
2. measured a fast and slow melting point of a known compound
3. measured a fast and slow melting point of an unknown compound.
4. measured the melting point for a mixture containing an unknown and two
other compounds that have similar melting points as the unknown.
5. used the results of the mixed melting points to determine the identity of an
unknown sample.


Prelab
In order to prepare for this lab copy the following items into your lab manual
(always work in ink). Title, Purpose (copied from the lab handout exactly), Prelab
questions (read Zubricks The Organic Chem Lab Survival Manual 8
th
ed. pg 88-
90, 99-103 and answer questions 1-4 found on pg 103). List apparatus and
materials. You also need a table of physical constants(see below), a summarized
background, a brief, summarized Procedure, Data Table (copied exactly, make
sure the spaces are large enough for you to record your data). Make sure you
update your table of contents in your lab notebook.


Physical Constants Table: You will need to prepare a table of physical
constants that includes the bp, mp, molecular weights, density, solubility,
and any other relevant data for each of the compounds used in the
experiment. This needs to be done for every experiment (CRC is available
as a reference). A copy of the CRC can be found in the library, but these
data can also be obtained from many different sources on line. Make
certain you cite the particular source used. For this experiment this will
include the benzoic acid and water. (See wccorganicchemguidelines
document for more information on what is required).



Background Information


The identification of a new organic compound is often a laborious and exacting
task. A known compound, on the other hand, usually may be identified (or
characterized) by the determination of one or more readily measurable physical
properties (melting point, boiling point, refractive index, infrared, ultraviolet, or
nuclear magnetic resonance spectrum, etc.) in conjunction with the examination of
a few chemical properties. For solid substances one of the most useful physical
properties is the melting point. The melting point of a substance is defined as
the temperature at which the solid and liquid phases are in equilibrium. The
melting point is described as the range of temperature over which a minute
amount of solid in a thin walled capillary tube first visibly softens and finally
completely liquefies. For the sake of simplicity, such melting point ranges are
called melting point (mp). The mp of a solid organic compound, if pure will be small
(1-2C), and the substance is said to melt sharply. The presence of impurities, even
in small amounts, usually depresses, or lowers, the melting point and widens the mp
range. Thus, the melting point is not only useful as a means of identification, but
also as a criterion of purity.


Melting points are usually determined by placing one or two milligrams of the solid
to be tested into a melting point capillary tube, and heating the capillary and a
thermometer together, and observing over what temperature range the material
melts. This tube is a thin-walled glass tube, about 100 mm in length and not more
than 2 mm in outside diameter, sealed at one end. The tube containing the solid is
then heated while the physical appearance of the solid is constantly observed and
both the softening temperature and completing liquefying temperature are
recorded and together give the mp for the solid.


A mixture melting point is useful in confirming the identity of an unknown
compound. A small portion of a known compound, whose melting point is known from
the chemical literature, is mixed with the unknown compound. If the melting point
of the mixture is the same as that of the known compound, then the known and the
unknown compounds are most likely identical. A decrease in the melting point of
the mixture and a broadening of the melting point range indicates that the
compounds are different.










Procedure


Part I Preparing the capillary tube and Apparatus - Instructor Demo


Make sure the sample is dry. [This is not an issue in this experiment, but in the
Future you will want to determine the melting point of a solid you have just
separated from a liquid using filtration. If you heat a solid that is damp this will
result in an inaccurate melting point.]
Place a small spatula tip (about full) of the solid on a watch glass and pulverize it
with the spatula until it is a powder. Form the powder into a mound and push the
open end of the capillary into the mound several times to force some of the powder
into it. You want between 1 and 2 mm (millimeters) of sample, lengthwise, in the
capillary. Holding the melting point tube between your thumb and forefinger, tap
the closed end against the bench top perpendicularly until the material is firmly
packed against that end of the tube. Repeat this process if you do not have enough
sample (1-2 mm) in the tube. If it is difficult for you to force the sample from the
open end to the closed end, try dropping the capillary onto a hard surface (closed
end down) through a section of plastic tubing instructor will demonstrate.
The sample should be well packed or it will not melt evenly. Insert your (dry)
thermometer into one of the small black bands you will find on the side bench. Push
the black band up the thermometer so it will be able to hold the capillary, near its
open end, to the thermometer with the closed end next to the thermometer bulb
(see Fig. 1). Pinch the black band and slide the top of the melting point tube under
it; then adjust the position of the capillary tube.
You will need to clamp the Thiele tube and the top of the thermometer to a ring
stand with clamps. Both the Thiele tube and thermometer should be vertical. The
thermometer should be centered in the Thiele tube with its bulb below the side-
arm of the Thiele tube. However, the thermometer and capillary tube must not
touch the Thiele tube (see Fig. 1). (If your clamp will not hold your thermometer,
you can attach the thermometer adapter and clamp to the rubber piece of that.
Safety tip: Be sure to lubricate the top of the thermometer with a small
amount of stopcock grease before attempting to slide the adapter onto the
thermometer. Do not force the adapter or you may wind up breaking the
thermometer and inserting its stub into your hand remember the safety
video?)
The Thiele tube is warmed using a Bunsen burner which heats the sidearm elbow
(see Fig. 1). This causes the oil to flow around the tube and past the sample and
thermometer bulb by convection, thus warming the sample and thermometer.
To obtain an accurate melting point you must heat the oil at a rate of 1 to 2
degrees per minute as you approach and go through the melting range of the solid.
If you heat too fast the bulb of the thermometer will not warm up as quickly as
the oil (but your solid will). Consequently, the thermometer and solid will be at
different temperatures resulting in an inaccurate mp range. If you have no idea
what the melting point of your solid is, you have two choices at this point:
(1) You could start at room temperature and warm at the recommended rate until
the solid melts. This could take more than an hour.
(2) You could start at room temperature and warm at about 10 degrees a minute
and obtain an approximate melting point. This is referred to as taking a fast mp.
Then, after the apparatus has cooled below the determined melting point, replace


the solid (and capillary) with a new one, and heat slowly (at a rate of 1-2C/min)
until the solid has melted, thus getting an accurate melting point. [Sometimes
materials decompose as they melt, so you should use a new solid for each new mp
determination.] Generally, this is the approach that is used.













Figure 1






Part II Calibration of Thermometer

1. Fill a beaker with crushed ice to a depth of about 10 cm (4 in). Add just
enough cold water to completely fill the voids between the pieces of ice and
barely float the mass of ice off the bottom of the beaker.
2. Immerse the bottom of your thermometer into the ice water mixture to a
depth of 7 or 8 cm.
3. Using the thermometer, stir the ice gently, and observe the drop in
temperature as shown by the thermometer. When the temperature stops
decreasing and has stabilized for 10 or 15 seconds, observe the temperature
displayed by the thermometer without removing it from the ice-water bath.
Record this temperature.
4. If the reading is within one Celsius degree of 0 C, the thermometer is fine
to use. If the reading differs from 0C by more than one degree Celsius,
return the thermometer to your instructor for a replacement.
5. If you get a replacement thermometer repeat steps 3 and 4 until an
acceptable thermometer is found. Dry the thermometer with a paper towel.


Part III Determining the Melting Point of a Known Compound: Benzoic acid.


1. Obtain 10 mg of benzoic acid (approximately of a spatula) and place on a
clean, dry watchglass.
2. Crush the sample and load two capillary tubes to 2mm. as described in Part I.
3. Set up Thiele tube as in Fig. 1 using one of the capillary tubes.
4. Take a fast melting point (rate of heating 10C/min.). Record the melting
point in Data Table I.
5. Cool the apparatus to 15C below the determined melting point of the 1
st

benzoic acid sample.
6. Using the 2
nd
capillary tube, take a slow melting point (rate of heating 1-
2C/min) to accurately measure the melting point of your sample. Record
the temperature at which the sample begins to soften as well as the
temperature at which the sample liquefies in Data Table I.
Part IV
Identification of an Unknown Solid Compound by Mixed Melting Point
Determination
1. Repeat steps 1-6 in Part III using the unknown sample assigned by your
instructor.
2. Record the number of the unknown and the results for both the fast and
slow melting point runs in Data Table 1.
3. From the table below, identify the two compounds that have melting points
closest to the melting point of your unknown compound.

Possible Compounds Melting Point (C)

Benzoic acid 122.4
trans-Cinnamic acid 133-134
Salicylic acid 157-159
2-naphthol 121-123
Urea 132.7
Citric acid 153



4. Record the names and melting points in your lab notebook.
5. Obtain a few milligrams of each of these compounds. Place one known
compound on a clean, dry, labeled watch glass. Add an approximately equal
amount of your unknown compound and mix. Load a new capillary tube to 2mm
with the mixture.
6. Similarly, place the other known compound on a second watch glass and add
an equal amount of your unknown compound to the same watch glass and mix.
Load this mixture to 2mm in another capillary tube.
7. Also, load two capillary tubes with the pure unknown.
8. Take the melting point of one of the mixtures and the pure unknown
simultaneously. Quickly heat the sample to within 30C of the pure
compounds melting point. Then slow the heating rate to 1-2C per min.
9. Record the melting point for the pure unknown and the mixture in Data
Table II.
10. Repeat the procedure using the other mixture.
11. Cleaning up: Place used capillary tubes in the waste container labeled Use
Capillary Tubes under the hood. Dispose of solid waste in container labeled
Organic Solid Waste under the hood. Wipe off/dry thermometers before
putting them away. Leave Thiele tubes on their ring stands and place entire
apparatus on the lab bench next to the large wooden cabinets. Wash and dry
glassware and return.


Thermometer reading in ice: _______________

Data Table I

Sample fast mp slow mp
Benzoic acid

Unknown solid #




List: Possible compounds to test and their literature mp

Test compound 1. lit. mp

Test compound 2. lit. mp

Data Table II

Sample Mp
Test compound 1 + unknown
Pure unknown

Test compound 2 + unknown
Pure unknown



Results


Proposed identity of compound is _______________________________



Discussion: Why did you choose the specific unknown? Comment on sources of error.
Comment on the usefulness of the mixed melting point data, and thermometer
calibration results.



Conclusion: State your unknown number, and the identity of the unknown.
Questions (to be copied into your notebook and then answered in your
notebook)

1. Briefly identify or explain:
(a) Why you were told to simultaneously measure the melting points of the
mixtures and of the pure unknown.
(b) Two useful functions served by knowing the melting point of an organic
compound
(c) Why a finely powdered sample should be used in a melting point
measurement
(d) Why it is important to heat a sample slowly to obtain an accurate melting
point
(e) What two effects a soluble impurity usually has on the melting point of a
compound.


2. A sample has an experimental melting point of 100 - 101C. Can you conclude
that the sample is pure? Briefly explain your reasoning.
3. An unknown compound melted at 131-133C. It is thought to be one of the
following compounds (mp, C): trans-cinnamic acid (133-134); benzamide (128-
130); DL-malic acid (131-133), or benzoin (135-137).
The mixture melting points of the unknown compound with each of the test
compounds are listed below. What is the unknown compound? Briefly explain
your reasoning.

Unknown plus mp range (C)
Trans-cinnamic acid 110-120
Benzamide 130-132
DL-malic acid 114-124
Benzoin 108-116


References: Cite source for physical constants.