International University Ho Chi Minh City –VNU

Deparment of Applied Chemistry

REPORT

ORGANIC CHEMISTRY LABORATORY

SEMESTER I (2023-2024)

EXPERIMENT 1
MELTING POINT DETERMINATION
Instructor: Dr. Le Quang Phong
Teaching Assistant: Nguyen Thanh Phong

Section: Wednesday Afternoon

Group 4:

1. Nguyễn Thị Cẩm Tiên BTBCIU20070

2. Nguyễn Hoàng Khánh Ngân BTBCIU20086
3. Đậu Ngọc Anh BTBCIU21042
4. Bùi Ngọc Mai BTBCIU21076
5. Trần Cao Bảo Ngọc BTBCIU21081
6. Đinh Thị Thanh Vân BTBCIU21016

Date of submission: Mar 27th, 2024

I. ABSTRACT
The main purpose of this experiment was conducted to determine the melting points of any
substances and melting point determination can ascertain their purity. The data for melting
temperature of pure materials, mixture compounds, and unknown substances was collected by using
the Capillary method which was applied by using Melting Point Apparatus throughout the
experiment. The results showed that the temperature of pure urea and cinnamic acid was about 1-2
°C higher than the standard melting temperature, while the compound mixtures with different molar
percentage ratios all had lower melting point compared to pure substances. Apart from that, the
melting temperature of the compound with the ratio 50:50 (at 98.1°C) reached the lowest levels
among 9 researched ratios. Furthermore, from determining the melting temperature of any unknown
substances, their characteristics and behaviors can be also found out. These findings indicated the
importance of melting point determination and the role of the capillary technique in the development
of various fields.

II. INTRODUCTION
In the solid phase, molecules are well-organized in a crystal structure by intermolecular forces such
as hydrogen bonds, dipole-dipole interactions, and the London dispersion force. However, this
crystalline array could be broken under a sufficient amount of energy, leading to the phase transition
from a rigid solid to a more freely liquid phase. The temperature at which the crystal changes into
the liquid form is called the melting point.

Melting point determination is a fundamental chemistry technique for identifying and characterizing
unknown substances. The focus of this experiment is to accurately identify the temperature at which
a substance undergoes a transformation from its solid form to a liquid state. Every substance has a
characteristic temperature that gives essential information about its identity and purity. The melting
temperature of a compound is not determined as an exact point but a narrow range of 0.5-1.0°C.
This melting range more typically fluctuates between 2-3ºC. When the sample is contaminated, the
impurity can disrupt the interactions between molecules in the structure. This interference could
reduce the required energy to overcome the crystal forces, which leads to a lower melting point of
the solid sample when the percentage of impurity increases. Thus, melting point determination is
useful not only in identifying an unknown sample but also in examining how pure a known
substance is. Consequently, a sample's purity can be ascertained by contrasting its melting
characteristics with the corresponding pure compounds. Several factors, including intermolecular

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interactions, impurities in the material, size and structure, and solid appearance, might affect the
melting point.

The capillary technique provided a rapid and accurate approach to detect the melting point in this
experiment. This procedure's primary principle is to put a minimal amount into a capillary tube with
one end shut. By attaching the sample tube to the stem of a thermometer center in a heating vessel,
the instrumentation warms the thermometer and the tube concurrently. The reference temperature
is higher than the setting temperature of this instrument's sample.

This experiment focused on investigating the melting points of pure substances, mixtures of
chemicals, and unidentified compounds using Melting Point Apparatus. The main objective is to
measure the melting points of urea and cinnamic acid combinations at different molar fractions. By
analyzing the melting points of these mixtures through a phase diagram in Figure 1, it is possible
to acquire a deeper understanding of how these compounds interact and behave when blended
together in different ratios. This information can provide valuable insights into the thermodynamic
properties and phase behavior of the compounds, shedding light on their solubility, crystal structure,
and potential applications in various fields.

Figure 1. Melting point phase diagram

III. MATERIAL & METHODS

1. Chemicals and equipment:
a. Chemicals:
In this investigation, the task of pinpointing and quantifying the melting point was accomplished
with the aid of substances such as cinnamic acid, urea acid, a sample of unknown composition, and
distilled water.

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b. Equipment:
The equipment utilized for this study comprised a mortar and pestle for pulverizing the substances, a
short melting bottle to store an unknown sample, capillary tubes for determining the melting point, a
device for measuring the melting point, and a balance for accurate weight measurements.
2. Procedure:
a. Determine the melting point of pure substances:
In the initial phase of the experiment, a pair of samples, each weighing 0.2g and consisting of urea
and cinnamic acid, were meticulously pulverized using a mortar and pestle. The resulting finely
milled powders were subsequently transferred into a capillary melting point tube to a depth of
between 2 and 3mm, with care taken to ensure the substance columns within the tubes were densely
packed at the bottom. Following the calibration of the apparatus to a temperature of 126°C, the
samples were introduced into the machine, leading to the successful determination of the melting
point.
b. Determine the melting points of the compounds mixture:
Volunteers were tasked with meticulously concocting mixtures of urea and cinnamic acid, employing
varying molar percentage ratios. These ratios spanned the spectrum from pure urea (100:0) to pure
cinnamic acid (0:100), with intermediate blends of 90:10, 80:20, and so forth. Each blend was
subjected to precise observation, recording the onset and completion temperatures of melting.
Subsequently, a graphical representation was crafted, correlating the melting temperatures with the
corresponding molar percentage ratios of urea and cinnamic acid.
c. Identify an unknown substance by melting point:
The task of discerning the melting point of an enigmatic sample would be given by instructors. It
was imperative to initiate a preliminary melting point assessment to ascertain a melting temperature
that was close to the actual value. Subsequently, the presumed identity of a mysterious sample was
validated by executing a blended melting point analysis alongside a genuine sample of the suspected
substance. Noticeably, if the materials matched identically, neither a reduction nor a broadening of
the melting point would occurred. Rest assured, an unknown sample would be aligned with one of
the compounds delineated in Table 1.

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 Table 1. Data regarding the melting points of potential unknown samples.

IV. RESULTS
Part 1: Determine the melting points of pure substances
Table 2. The melting point of urea and cinnamic acid in form of pure substances

Substances Melting point Observation

The melting point was quite higher but overall still close to
Urea 134.5oC
the critical range of 131-133oC

The melting point was much higher but overall still close to
Cinnamic acid 135.2oC
the critical range of 131-133oC

Part 2: Determine the melting points of mixture

Table 3. The melting points of the mixtures of urea and cinnamic acid according to different mole
ratios

Ratio Urea Cinnamic acid Adjusted Melting point

(Urea/Cinnamic acid) (g) (g) temperature (°C) (°C)

100: 0 1 0 126 134.5

90:10 0.78 0.22 118 128.1

80:20 0.62 0.38 109 121.0

60:40 0.38 0.62 97 118.3

50:50 0.29 0.71 98 98.1

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 40:60 0.21 0.79 105 104.8

20:80 0.09 0.91 106 120.7

10:90 0.04 0.96 121 125.7

0: 100 0 1 122 135.2

Figure 2: The melting points of the urea and cinnamic acid mixtures with different ratios
The mixtures of urea and cinnamic acid with different ratios decreased gradually from 100:0 to
50:50 which reached the lowest melting temperature. In addition, the melting temperature of
mixtures was lower than that of pure substances.
Part 3: Identify the unknown substances by melting point
The melting point of the unknown sample was 116.2oC. It was determined as Fluorene when
compared with the melting point table given in the lab manual.

V. DISCUSSION

As the theoretical melting point of urea and cinnamic acid was 131-133°C, the adjusted temperature
was set to 126°C, which was 5°C lower than the critical point, to avoid overshooting and inaccurate
reading temperature. The observed result for the melting point of urea and cinnamic acid was 1-2°C

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higher than the standard values, at 134.5°C and 135.2°C, respectively. This result could be
acceptable in unstrict requirements since the difference between the theoretical and experimental
melting temperatures was insignificant.

In the melting point determination experiment, insufficient grinding of the crystals can result in
higher observed melting temperatures due to the need for more energy to melt the sample fully.
Errors in the instruments, such as the melting point apparatus and capillary tubes, can also affect
the accuracy of the measurements. In the experiment of melting point determination, the
contamination could be mentioned as a reason for inaccurate results since the impurities can lower
the melting point value. However, as the observed melting temperature was higher than the
theoretical one, the contamination might not contribute to the error in the experiment.

Melting points of the nine ratios of urea and cinnamic acid were used to construct a phase diagram,
which ultilized to determine composition of an unknown mixture. In the mix of two components,
each chemical acted as an impurity on the other. As shown in Figure 2, the two highest points of
melting temperature were of the pure samples of urea and cinnamic acid, at 134.5°C and 135.2°C,
respectively. The melting temperature of samples was then dropped, correlating to the increase in
the impurity ratio. The lowest melting temperature the mixture could get was called the eutectic
point.

An ideal phase diagram was expected to have two downtrend curves beginning from 100:0
composition (pure compound) and converging at the eutectic point. Based on Figure 2, the melting
points of nine urea/cinnamic acid mixtures were arranged in trend, resulting in the possibility that
the constructed phase diagram was reliable enough to determine the composition of an unknown
urea and cinnamic acid mixture. Since measuring the melting points of mixtures of various
compositions was conducted, errors in any measurement can significantly impact the accuracy of
the melting point phase diagram. Except for two pure samples of pure urea and cinnamic acid, any
other compositions should be mixed carefully before grinding finely to ensure the sample put into
a capillary tube was in the exact measured ratio. Additionally, the solid in the sealed end of the
capillary tube should be 2-3 mm in height and kept approximately the same in different
measurements to avoid inconsistency.

For the final part of the experiment, an unknown sample was identified by melting point
determination. Numerous factors, including atom arrangement, configuration, molecular geometry,
and intermolecular interactions, contributed to the melting temperature and molecules with similar
structures often exhibited similar melting ranges. It was also notable that impurities could
significantly affect the melting range of a pure compound, causing it to become broader and lower.

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A two-step process was essential for material identification. The unknown sample's melting point
was initially measured to predict its identity, which was then confirmed by measuring the melting
point of the mix between the unknown and suspicious chemicals. The matching melting point
suggested identical structures, indicating the compounds are likely the same. Conversely, a lower
melting point in the mixture indicates that the unknown differs from the predicted compound,
precluding its identification as such.

The melting point of the unknown sample 4 was observed at 116.4°C, falling within the melting
range of Fluorene, a suspicious compound with a melting range of 114-116°C. Thus, it was
hypothesized that the unknown sample was Fluorene. Unfortunately, due to the laboratory section's
time limitation, the hypothesis could not be double-checked by measuring the melting point of the
mixture of the unknown sample and the predicted compound. Therefore, the reliability of the
conclusion remained uncertain, with potential errors similar to those encountered in the previous
two melting point experiments on known pure compounds and mixtures.

One of the greatest mistakes mentioned was the grinding process, where the sample may not have
been finely ground before being introduced into the capillary tube. In addition, contamination
should also be considered as the melting temperature of a pure compound was easily lowered due
to the effect of impurities on disrupting the interactions. Hence, moisture from the environment,
dust, and contamination of other compounds sticking on the experimental instrument could
contribute to the error of this identification.

With the advancement of technology, several methods have been developed to improve melting
point determination's precision, speed, and simplicity. Since the capillary method relies on the law
of melting point depression, various factors, such as particle size, purity, and stability in the sample
size, could considerately affect the accuracy of the measurement. The step-mode scanning technique
using differential scanning calorimetry (DSC) introduced by Grant M. Gustin can help minimize
the effects of the sample and instrumental conditions on accuracy by computing the second
derivative of the melt data. Furthermore, compared to the melting point determination method,
many modern chromatographic and spectroscopic techniques have been utilized to obtain more
precise chemical identification and purity verification results.[3][4]

VI. CONCLUSION

The capillary method proved to be a valuable tool in the field of melting point determination. Its
ease of use, precision, and versatility made it indispensable for identifying compounds and assessing
their purity. When impurities were present, they caused a reduction in the melting point, resulting

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in a lower temperature at which the mixture melted. In this particular experiment, the melting point
of pure substances was closely aligned with both theoretical and empirical data. However, when
dealing with complex mixtures, errors in data were sometimes introduced due to subpar techniques.
Additionally, the narrow melting range of these compounds meant that any of these variables could
lead to an inaccurate prediction for an unknown sample. Ultimately, the quality of the sample itself
emerged as one of the most critical factors that directly influenced the results, necessitating proper
sample preparation. Despite these challenges, the capillary technique remained an essential tool for
characterizing and analyzing different chemicals in laboratories and educational institutions,
contributing to advancements in materials science, chemistry, and pharmaceuticals.

VII. REFERENCE
[1] Son, H. L. (2022). Melting point determination. Organic Chemistry Lab Manual (pp. 04-06). Ho
Chi Minh City: International University, HCMC.

[2] Yalkowsky, S. H. (2014). Carnelley’s rule and the prediction of Melting Point. Journal of
Pharmaceutical Sciences, 103(9), 2629–2634. https://doi.org/10.1002/jps.24034

[3] van Dooren, A. A., & Müller, B. W. (1984). Purity determinations of drugs with differential
scanning calorimetry (DSC)—A critical review. International Journal of Pharmaceutics, 20(3),
217–233. https://doi.org/10.1016/0378-5173(84)90170-4

[4] Gustin, G. M. (1980). Broad range purity analysis by melting point depression using a singular
feature common to all DSC purity scans. Thermochimica Acta, 39(2), 81–93.
https://doi.org/10.1016/0040-6031(80)80001-3

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VIII. LAB NOTE

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