Melting Point Determination

Identity and Purity of Solid Organic Compounds

Objectives
To introduce the technique of melting point determination.
To use the concept of melting points for identification and characterization of
organic compounds.
Properly fill and use a capillary melting point tube.
Determine accurate melting point ranges for a ide !ariety of organic
substances.
Introduction
The melting point of a solid can easily and accurately be determined using only
a small amount of material. In combination ith other measurements" melting point
information can pro!ide rapid confirmation of the identity of un#non substances.
The method of capillary melting point determination in!ol!es placing a small amount
of sample in the bottom of a narro capillary tube that has been closed at one end.
The melting point is then determined using a melting point apparatus $%igure &' that
simultaneously heats both the sample tube and a thermometer. The temperature range
o!er hich the substance melts is recorded.
(elting is said to begin hen the first indication of liquid is seen. The end of
the melting point range is the temperature at hich all of the solid material has
become a liquid.
Some pure materials possess a !ery narro melting range" perhaps as little as
).*+&.)
,
C" hile more typically a -+.
,
C range ill be obser!ed. /ou ill usually see
data recorded as" for e0ample" mp -.-+-.1
,
C. Though formally denoting the melting
range" this piece of data is almost uni!ersally referred to as the melting point $mp'.
%or the most accurate results" the rate of heating should be kept relatively low"
especially for lo+melting samples" to ensure that the thermometer reading represents
as accurately as possible the true temperature e0perienced by the sample tube $since
the transfer of heat ithin the apparatus is relati!ely slo'. 2ith this fact in mind" it is
sensible hen recording a melting point of an un#non material to perform a trial run
here the temperature range is increased relati!ely rapidly in order to ascertain a
rough melting range. The determination is then repeated by heating rapidly to ithin
around tenty degrees of the e0pected melting point and then !ery carefully
increasing the temperature the remaining fe degrees until the melting point is
reached.
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Figure 13 4pparatus for manual melting point determination.
5(el+temp5 de!ice $left' and hot oil method $right'.
4lthough a pure solid might be e0pected to ha!e a single" sharp melting point"
most samples are obser!ed to melt o!er a narro range of a fe degrees Celsius. The
obser!ation of a melting range may be a result of inhomogeneities in the macroscopic
nature of the solid sample" or may indicate the presence of other substances in the
sample $contaminants or by+products of the method used to prepare the materials.

(elting Points as Criteria of Purity. Thermodynamics tells us that the freezing point of
a pure material falls as the amount of an impurity is increased. The presence of an
impurity in a sample ill both lower the obser!ed melting point and cause melting to
occur o!er a broader range of temperature. 6enerally" a melting temperature range of
).*+&.)
,
C is indicati!e of a relati!ely high le!el of purity. It follos that for a material
hose identity is #non" an estimate of the degree of purity can be made by
comparing melting characteristics ith those of a pure sample.
(elting Points as a (eans of Identification and Characterization. %or pure samples a
clear difference in melting points beteen to materials re!eals that they must
possess different arrangements of atoms" or configurations. If to materials are found
to ha!e the same melting point then they may" but not necessarily" ha!e the same
structure. Clearly" the recording of a melting point is a desirable chec# of purity and
identity but must be combined ith measurements from other analytical techniques in
order to unambiguously identify a material and assess its purity. Part of the need for
additional !erification deri!es from the sub7ecti!e nature of capillary melting point
determination. 8!en hen heating is !ery finely controlled" to ensure consistency of
sample and thermometer temperature" then the human element of !isual inspection of
the melting point introduces significant !ariation.
(i0ed (elting Points. (i0tures of different substances generally melt o!er a range of
temperatures that concludes at a point belo the melting point of either of the pure
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components + each component acts as an impurity in the other. To pure substances"
ith sharp melting points" can be shon to be different by mi0ing them and recording
the lowered melting point range. This type of e0periment pro!ides a means by hich
to confirm a proposed identity for an un#non sample. If a sharp melting point is
obser!ed for a mi0ture of the un#non ith a genuine sample then it is highly li#ely
that the samples are identical.
(elting Points and (olecular Structure. (elting points are notoriously difficult to
predict ith any accuracy or confidence. Systematic !ariations of melting point ith
!ariation in structure are not as ob!ious or predictable as ith boiling point. 9oe!er"
the sometimes surprising !ariations are often only highlighted in !ery closely related
molecules and the ob!ious general rule can be applied3 melting points do generally
increase ith increasing molecular eight.
The difficulties in!ol!ed in predicting melting points are a result of the problems
associated ith predicting molecular pac#ing in crystals. (any" potentially
conflicting" factors play a role in determining melting points including molecular
shape" interactions beteen groups ithin the molecule" and the degrees of freedom
the molecule possesses ithin the crystal.
There are three e0periments to perform today.
Part A: Melting Points of Urea and Succinic Acid
&. Determine the melting point range of urea" then the melting point range of
succinic acid .
-. The capillary melting point tubes should be filled by crushing the sample to a fine
poder on a atch glass ith the end of a glass rod and then introducing this poder
to the tube by pressing the open end into the podered sample + 4s# your instructor
for help" if you need it. $see the note belo'.
.. Once a 1+* mm depth of poder has been introduced" the tube should be turned
o!er. Tap the sealed end of the tube on a hard surface to compact all of the material at
the bottom.
1. 4ssemble the melting point apparatus as in the figure abo!e.
5. :ecord the melting point range of both urea and cinnamic acid.
Part B: Mied Melting Points
&. (i0tures of urea3 succinic acid in &3. and .3& ratios $by mass' ha!e been
prepared.
-. :ecord the melting point range of the &3. ratio sample and then record the melting
point range of the .3& ratio sample.
.. ;ualitati!ely" note the melting beha!ior of these mi0ed samples as compared to
those of the pure samples.
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Part !: Un"no#n Identification
&. 8ach student should determine the melting point range of an un#non.
-. Obtain an un#non sample from your instructor or T4 $remember + a quic#" crude
run can be !ery helpful'.
.. Determine the melting point range of the un#non.
1. %rom the melting point range" using the table belo to determine the identity of
the un#non.
*. Confirm the identity of your sample by performing a mi0ed melting point
determination ith an authentic sample of the suspected material + remember" the
melting point ill not be lowered or broadened if the materials are identical<<
=. 2hen finished" discard all melting point capillary tubes in the glass trash.
!om$ound Melting %ange&
'
!
4cetanilide &&..*+&&1
Salicylic 4cid &*>.*+&*?
Sulfanilamide &=*+&==
@enzoic 4cid &-&.*+&--
p+Terphenyl -&)+-&&
Melting Point Determination
:eport Sheet
7
Name:---------------------
-
Part A: Melting Points of Urea and Succinic acid
(elting :ange (elting :ange
Trial & Trial - $if needed'
Succinic acid ++++++++++++++++ +++++++++++++++
Area ++++++++++++++++ +++++++++++++++
Part B: Mied Melting Points
(elting :ange (elting :ange
Trial & Trial -$if needed'
&3. ratio
Area3 succinic acid ++++++++++++++++ +++++++++++++++
.3& ratio
Area3succinic acid ++++++++++++++++ +++++++++++++++
Description of melting beha!ior of mi0ture $compared to pure compound'3
Part !: Un"no#n Identification


(elting :ange (elting :ange
Trial & Trial - $if needed'
+++++++++++++++ +++++++++++++
An#non letter3 A " B " or !.
An#non Identity3 +++++++++++++++++++++++++++++++
(uestions:
&. Define the 5melting point5 of a substance.
8
-. 2hat is the purpose of determining melting pointsB
.. 2hy could the rate of heating influence the melting pointB
1. 2hy should samples for melting point determination be finely poderedB
*. 2hy is this method not used for finding the melting points of inorganic
compoundsB
=. pentane is a linear carbon al#ane that has a melting point of about &-?.>,
C.Dimethylpropane $neopentane' is a branched carbon molecule " it has a
melting point of +&C, C. 2hat is the origin of this remar#able differenceB
9
)ote
See 9o to fill the melting point capillaries

1* Pac# the capillary tube by pressing the open end gently into a sample of compound to be
analyzed. Crystals ill stic# in the open end of the tube.
+* The solid should fill the tube to a depth of -+. mm. Tap the bottom of the capillary on a hard
surface so that the crystals pac# don into the bottom of the tube.
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