You are on page 1of 7

Clarissa A.

Gomez Group 4

CHE-3

CHM141L-A01

EXPERIMENT 1

PHYSICAL CONSTANTS OF SOLID AND LIQUID AND ORGANIC COMPOUNDS

The first experiment deals with the effect of intermolecular forces of attraction in relationship with the
melting point or boiling point of a certain compound. The first part of the experiment incorporated the obtaining
of the melting point of an unknown solid. The melting point of a compound is the temperature at which the solid
is in equilibrium with its liquid. A solid compound changes to a liquid when the molecules acquire enough energy
to overcome the forces holding them together in an orderly crystalline lattice. For most organic compounds, these
intermolecular forces are relatively weak. The melting point range is defined as the span of temperature form
which the crystal first begins to liquefy to the point at which the entire sample is liquid. Most pure organic
compounds melt over a narrow temperature range 1-2 0C.1

The presence of a soluble impurity always causes a decrease in the melting point expected for the pure
compound and a broadening of the melting point range. In order to understand the effects of impurities on
melting point behavior, we consider the eutectic point for two different fictitious organic compounds. A eutectic
system is a Mixture of chemical compounds or elements that has a single Chemical composition that solidifies at a
lower temperature than any other composition. On a Phase diagram (Figure 1) the Intersection of the eutectic
temperature and the eutectic composition gives the eutectic point. The phase diagram at right displays a simple
binary system composed of two components, A and B, which has a eutectic point. The phase diagram plots relative
concentrations of A and B along the X-axis, and temperature along the Y-axis. The eutectic point is the point at
which the liquid phase borders directly on the solid α + β phases (the solid forms of pure A and B), representing the
minimum melting temperature of any possible alloy of A and B. The temperature that corresponds to this point is
known as the eutectic temperature.2

Figure 1: Phase Diagram


Because the melting point of a compound is a physical constant is useful in determining the identity of the
unknown compound. A good correlation between the experimentally measured melting point of an unknown
compound and the accepted melting point of a known compound suggests that the compound may be the same.
However, many different compounds have the same melting point. 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 a 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.3

In preparing the sample, we pack the tube by pressing the end gently into a pulverized sample of the
crystalline material. Then to ensure good packing, we drop the capillary tube with the open end up through a 1-m
long piece of glass tubing and repeat it for several times until the crystals are transferred to the close end of the
capillary tube. However, there are other electrical instruments used in measuring melting points. One example is
the Thiele Tube. The Thiele tube (Figure2 a), named after the German chemist Johannes Thiele, is laboratory
glassware used to contain and heat bath oil. Such a configuration is commonly used in determining the melting
point of a substance. This is filled to the base of the neck with silicone oil or mineral oil. The capillary tube is
attached to thermometer so that the sample is located next to the middle of the thermometer bulb. The
thermometer is inserted into the oil and then the side arm of the Thiele tube is heated with a Bunsen burner
flame. Thomas-Hoover Uni-Melt device (Figure 2 b) is another instrument that contains silicone oil that is stirred
and heated electrically. Silicone oil can be heated to temperatures up to 250 0C. With this device, up to seven
samples can be analyzed at one time. Another one is the Melt-Temp apparatus (Figure 2 c) consists of an
aluminum block that is heated electrically. The aluminum block can be heated easily to temperatures up to 400 0C,
can tolerate temperatures up to 5000C for brief time periods. A thermometer up to three samples can be inserted
into the block at one time. A light and magnifier permit easy viewing of the sample(s). 4

(a) (b) (c)

Figure 2: Different types of Melting Point


Apparatus (a.) Thiele tube (b.)
Thomas-Hoover Uni-Melt (c) Melt-Temp
If the melting point of the compound is unknown, in order to save time an approximate MP is first
determined by heating the sample fairly rapidly. Once the approximate MP is known, a more careful determination
is made on a fresh sample. Note that once a sample has been melted, it may have decomposed slightly.
Contamination with decomposition product will change the MP of the sample, so a fresh sample must always be
used for each determination.5

Error in observed melting points often occurs due to a poor heat transfer rate from the heat source to the
compound. Sometimes slight changes, such as shrinking and sagging, occur in the crystalline structure of the
sample before melting occurs. To avoid these possible error, a large majority of pure organic compounds melt
neatly within a range of 1.5 ºC or melt with decomposition over a narrow range of temperature (≈2 ºC) at heating
rates below 0.5 ºC/min. 3 Although many substances melt cleanly and can be melted, crystallized, and melted again
repeatedly without chemical decomposition, others chemically decompose before they melt, forming substances
of lower molecular weight. The temperature of decomposition is just as useful as the melting point in physically
characterizing a substance. Decomposition is usually signaled by a color change; for example, white substances
invariably start to turn brown near the decomposition temperature. The temperature at which the color change is
first observed signals that the substance is approaching the decomposition temperature at somewhat higher
temperature, liquid may form. At this temperature or at an even somewhat higher temperature, gas bubbles may
be seen if gaseous decomposition products are formed. All of these temperatures aid in characterizing a
substance, so all should be noted and reported.6 Some compounds decompose at or near their melting points.
This decomposition is usually characterized by a darkening in the color of the compound as it melts. If the
decomposition and the melting occur over a narrow temperature range of 1-2 0C, the melting point is used for
identification and as an indication of sample purity. The melting points of such compound are listed in the
literature accompanied by d or decomp. Some compounds pass directly from solid to vapor without going through
the liquid phase, a behavior called sublimation. When sublimation occurs, the sample at the bottom of the
capillary tube vaporizes and recrystallizes higher up in the capillary tube. A sealed capillary tube is used to take the
melting point of a compound that sublimes at or below its boiling point. The literature reports the melting point
for these compounds accompanied by s, sub or subl.7

Table 1: Melting Point Determination

Trial 1 Trial 2
Initial Temperature 0C 129 128
Final Temperature 0C 131 130

In the experiment, we recorded as the initial temperature at which the crystals first begin to melt and the
final temperature at which the last trace of crystals melts. Based on the data we gathered, the melting range of the
unknown substance is 128.5-130.5 0C. From the list of our researched compounds, the nearest possible identity of
the unknown compound is urea. We concluded this because urea has a melting point range of 132-135 0C and
with a appearance of white crystals and white powder which is exactly the appearance of the unknown sample.
However, the temperature of the unknown is almost 2 0C lower than the real melting point range of urea.. With
this, we can say that the unknown substance is an impure sample of urea.

The second part of the first experiment deals with the boiling point determination. The boiling point of a
liquid is the temperature at which that liquid is converted to a gaseous state. Boiling point is formally defined
as the temperature at which the vapor pressure of the liquid becomes equal to the pressure at the surface of
the liquid. The boiling point of a liquid can change if the pressure at the liquid's surface changes. The normal
boiling point of a liquid is the constant temperature at 1 atmosphere of pressure at which the liquid changes
into a gas.
If a sample of a liquid is placed in an otherwise empty space, some of it will vaporize. As this happens, the
pressure in the space above the liquid will rise and will finally reach some constant value. The pressure under
these conditions is due entirely to the vapor of the liquid, and is called the equilibrium vapor pressure. The
phenomenon of vapor pressure is interpreted in terms of molecules of liquid escaping into the empty space
above the liquid. In order for the molecules to escape from the liquid phase into the vapor phase, the
intermolecular forces (have to be overcome which requires energy. Since the nature of the intermolecular
forces is determined by the molecular structure, then the amount of energy required to vaporize the sample
also depends on the molecular structure. As the number of molecules in the vapor above the liquid becomes
larger, the rate of return of the molecules from the vapor to the liquid increases until the rate of return is
equals the constant rate of escape. This is the equilibrium condition and the corresponding concentration of
molecules in the vapor space gives rise to the equilibrium vapor pressure. At higher temperatures, the greater
average kinetic energy of the molecules in the liquid results in a greater constant rate of escape. Equilibrium is
established at higher temperatures, and so larger numbers of molecules are present in the vapor phase and
the pressure is higher. When the vapor pressure of a liquid is equal to the atmospheric (or applied) pressure
then boiling occurs. The temperature, at which this occurs, for a given pressure, is the boiling point. 8 The
boiling point of a liquid is sensitive to atmospheric pressure, and varies directly with it. As atmospheric
pressure decreases, the boiling point will drop; at approximately normal pressure it will drop about 0.5 0C for
each 10-mm Hg drop in pressure. At much lower pressures, close to 10 mmHg, the temperature will drop
about 10 0C when the pressure is halved.9

At lower pressures, a boiling point nomograph or temperature-pressure alignment chart (shown below)
can be used to determine the boiling point. The basic principle is that a line through two known points on any
two different scales (A, B,C) can be used to read off the value on the third scale. There are two ways in which a
pressure nomograph can be used (i) to determine the boiling point at atmospheric pressure (760 mm Hg)
given the boiling point at a lower pressure and (ii) to determine the boiling point at a lower pressure given the
o
boiling point at atmospheric pressure. First, let's say we have a compound with a boiling point of 100 C at
o
1mm Hg pressureTo know the boiling point at 760 mmHg, we need to draw a line from 100 C on scale A (left
side, observed boiling point) to 1.0 mm Hg on scale C (right side, pressure "P" mm). We can then read off the
o
boiling point at 760 mm on line B, it is about 280 C.
Figure 3 A : Using a pressure nomograph:
Determining the boiling point at 760mm
Hg (scale B) for a sample that boils at
o
100 C (scale A) at 1mm Hg (scale C)

Now what temperature would that same compound boil at 10 mm Hg pressure? Now we draw a line that
o
passes through 280 C on scale B (middle scale, the boiling point at 760mm Hg) and to 10mm Hg on scale C. By
extending that line to scale A, we can read off the new boiling point on scale A (left side) as being about
o
140 C.10

Figure 3 B : Using a pressure nomograph:


Determining the boiling point (scale A) at
10mm Hg (scale C) for a sample that boils
o
at 280 C at 760mm Hg (scale B)
In the experiment we executed, the Thiele tube is heated with a small flame as if one were determining a
melting point (see above). There is an initial stream of bubbles as dissolved air is expelled and then, a

little later, a rapid and continuous stream of bubbles emerges from the inverted capillary tube. At this point
stop heating. Soon the stream of bubbles will slow down and stop. When they stop, the liquid will enter the
capillary tube. The moment when the liquid enters the capillary corresponds to the boiling point of the
liquid, and the temperature is recorded.
The explanation of this method is a reasonably simple one. During the initial heating, the air trapped in the
capillary tube expands and leaves the tube and vapor from the liquid also enters the tube. There is always
vapor in equilibrium with a heated liquid. This gives rise to the initial stream of bubbles. When the
temperature reaches the boiling point, the vapor pressure inside the capillary tube equals the atmospheric
pressure. As the temperature rises just above the boiling point then the vapor will start to escape: the
second set of bubbles.
Two problems are common to this method. The first arises when the liquid sample in the small test
tube is heated so strongly that it evaporates or is boiled away. Once the oil has cooled, add more liquid
sample to the small test tube and resume heating but more gently. The second arises when the liquid is not
heated above its boiling point. If the heating is stopped at any point below the boiling point of the liquid, the
liquid will enter the tube immediately. It will enter the tube because the trapped vapor will have a pressure
less than that of the atmosphere.11

Table 2:Boiling Point Determination

Trial 1 Trial 2
Initial Temperature 0C 70 70
Final Temperature 0C 75 75

Based on the data from the second table, the boiling point ranges from 70-75 0C. The nearest boiling point
of a substance that is possible is ethyl acetate with a clear liquid appearance. However, the real boiling
point of ethyl acetate is 77 0C which is greater than the boiling point of our unknown solid. Through this we
can say that the sample is an impure ethyl acetate.
References:
1,3,4,7,11
Lefevre, Joseph W. Measuring the Melting Points of Compounds and Mixtures. Web. July 3, 2010.
2
http://www.myhomefoundry.com/casting_info/eutectic-point.pdf
5
http://www.chem.umass.edu/~samal/269/mp.pdf
6,8,9,10
Melting Point Determination. Stanford Research Systems. July 3, 2010

http://www.wpi.edu/Academics/Depts/Chemistry/Courses/General/meltingpoint.html

http://www.wpi.edu/Academics/Depts/Chemistry/Courses/General/meltingpoint.html

http://www.cerlabs.com/experiments/10875407013.pdf

http://www2.bakersfieldcollege.edu/mdaniel/ch2a/ppt/VPressure.htm

You might also like