Experiment 5: Boiling Point and Melting Point Determination Kathrine Grace Capistrano, Windale Anne Delos Santos, Ehcel

Hurna Group 5, Chem 31.1 SAD, Mr. Nathaniel Carolina August 27, 2011 I. Abstract Organic compounds exhibit physical and chemical properties. These properties are a consequence of their structure. Boiling point and melting point are physical properties of organic compounds and are affected by several factors (intermolecular forces of attraction, molecular size, degree of branching, molecular symmetry, intramolecular H-bonding, and polarizability). Experiment 5, Boiling Point and Melting Point Determination, consists of two parts which aims to identify the effect of impurities to the melting point and boiling point of organic compounds and the forces that operate in these types of reactions. Melting point ranges of benzoic acid and benzoic acid-urea mixture for Part A and boiling points of the two distillates from Experiment 4 and hexane for Part B were determined by using a setup consisting of capillary tubes attached to a thermometer immersed in an oil bath. Results have shown that benzoic acid-urea mixture has a lower and broader melting point range than benzoic acid and the distillate from fractional distillation has a lower boiling point from the distillate from simple distillation. As such, impurities alter the boiling point and melting point of a substance. Thus, these particular properties can be useful in product characterization and purity determination. II. Keywords: Boiling Point, Melting Point, Interparticle Forces of Attraction (IPFA) III. Introduction Boiling and melting points are physical properties of liquids and solids that can be used to estimate the purity, determine the identity of the liquid or solid, and establish non-identity of substances. Impure liquids and solids tend to have lesser boiling point and wide melting point range compare to pure samples. Boiling point is the temperature at which the liquid turns into a gas. Melting point is the temperature at which a solid is converted into liquid. The boiling point of a liquid and the melting point of a solid are determined by the strength of the interparticle forces of attraction, or IPFA. Molecules are held together by different forces, such as ionic attraction, van der waals forces, dipole-dipole attractions and hydrogen bonds. Boiling a liquid and melting a solid involve the breaking of these bonds, hence, the stronger the forces of attraction, the higher the boiling point or melting point of a substance. Thus the strength of the forces of attraction determines the boiling and melting point. Organic compounds are covalently bonded, and thus usually exhibit lower boiling and melting points than the inorganic substances that exhibit ion-ion interaction. The factors that affect the boiling and melting points of organic substances are: molecular size, branching, polarity, molecular symmetry and intramolecular H-bonding. Larger molecules boil or melt at higher temperatures. As the molecular weight increases, the hydrocarbon chain gets longer therefore LDF gets stronger. Branched molecules exhibit lower melting and boiling points than their corresponding linear structures. As the molecules become branched, CHEM31.1 Organic Chemistry they tend to become more spherical; therefore there is less area for interaction. Greater polarity also means higher boiling or melting points. Higher polarity translates to greater interparticle force of attraction, thus it is harder to break the bond. Asymmetrical structures exhibit higher melting and boiling points than their symmetrical counterparts. The dipole moments of symmetrical compounds cancel out as compared to their asymmetrical counterparts. However the melting point increases due to a better packing of units when molecules are symmetrical. Intramolecuar H-bonding decreases boiling and melting points. Intramolecular Hbonding prevents interaction between molecules as polar groups engage in interaction within the molecule. The objectives of this experiment are to learn the methods used to get the melting point of solids and boiling point of liquids; determine the effect of impurities in the melting and boiling point of substances and to identify the certain forces that influence melting and boiling point. It is important for students to learn the physical properties, boiling point and melting point, as they are unique properties of substances. It can also be used as a toll to determine the purity of a substance. IV. Experimental Part A. Melting Point Determination of Benzoic Acid and Benzoic Acid-Urea Mixture Two capillaries were sealed in one end. 0.5g benzoic acid was powdered using mortar and pestle and was introduced into the first capillary by pushing it on one end and by tapping the closed Page 1 of 4

end on the tabletop. It was filled to about 1cm in height. Another 0.5 g sample of benzoic acid with an added pinch of urea was pulverized and was introduced to the second capillary tube, also occupying a height of about 1cm. The two capillaries were attached to the thermometer by a string. The capillaries were placed in a beaker with 10mL cooking oil separately. Each was heated and the temperature at which the sample starts to liquefy and the temperature at which the solid has completely melted was recorded.

this case, the lower end of the melting point ranges of benzoic acid and benzoic acid-urea mixture is 37C and 48C respectively. The higher end of the melting point range is the temperature at which the solid has completely melted the temperature at which the last solid disappears. The higher end of the melting point ranges of benzoic acid and benzoic acid-urea mixture is 149 C and 83 C. Theoretically, the melting point range of benzoic acid-urea mixture should be lower than that of the benzoic acid.

Table 1. The observed melting point ranges of samples. Figure 1. Melting Point Determination Set-up

B. Boiling Point Determination The extracted boiling point of hexane is 64 C. The theoretical value is 69 C. The distillate from the simple distillation yielded a boiling point of 100-140 C while the distillate from fractional distillation yielded a boiling point of 122-105 C. The boiling point of the samples must be of a single value only since organic compounds tend to have distinct boiling points. Theoretically, the distillate from the fractional distillation must have a lower boiling point than that of the distillate from the simple distillation. The result is accurate if the temperatures of 105 C and 140 C were to be considered.

Part B. Boiling Point Determination of Distillate and Hexane Three capillaries were sealed in one end. 10 drops of hexane was introduced into a 5-mL test tube. After which, the test tube was attached to the thermometer. The capillary tube was introduced into the test tube containing hexane with the open end immersed in the liquid sample and was heated in an oil bath. After having observed a rapid and continuous stream of bubbles, the flame was removed and the bath was allowed to cool. The temperature reading when the bubbles stop to come out of the capillary and the temperature reading just before the liquid sample enters the capillary tube were recorded.

Table 2. The observed boiling points of samples.

Figure 2. Boiling Point Determination Set-up

Deviations from the true value may be a result of improper technique or contamination of the sample. VI. Discussion Melting point is the temperature at which the first crystal liquefies until the temperature at which all the crystals has turned into liquid. Thus, the melting point is actually a range. Measurements Page 2 of 4

V. Results A. Melting Point Determination

The lower end of the melting point range is the temperature at which the sample starts to liquefy the temperature at which the first liquid is seen. In CHEM31.1 Organic Chemistry

of the melting point can provide information about the purity of a substance. Pure substances tend to have sharp melting point ranges. Meaning, it has a narrow range, occurring over a 0.5-1 C temperature range. Their melting points are often expressed in single values. Impure substances have a tendency to cover a broader range, having a melting point of greater than 5 C. Their melting points are expressed in ranges, having a lower and an upper end. Theoretically, the melting point range of the benzoic acid-urea mixture must be lower and broader than the melting point range of benzoic acid. Solid crystals are arranged in a tightly packed crystal lattice. Various intermolecular forces hold the molecules together. In order for a substance to melt, these forces must be overcome. The energy to disrupt the crystal lattice is supplied in the form of heat. As heat is applied, the vibrational energy of the molecules increases until it exceeds the lattice energy, thus, breaking the crystal lattice. The highly ordered molecules in the solid are converted into a more random arrangement of molecules in the liquid. Impurities affect the melting point of a substance by depressing it. In this case, the urea serves as the impurity. Impurities prevent the molecules from forming a crystal lattice by disrupting the repeating pattern of forces that holds the particles together. Therefore, a smaller amount of energy is needed to melt the part of the solid surrounding the impurity since the molecules are already disrupted. Thus, the more impure the solid is, the more its structure is disrupted, and the lower the melting point is. As such, melting point is also helpful in estimating the identity of an unknown compound through a procedure known as mixed melting point. For example, if there are two solid samples, one known and one unknown, one can conduct a mixed melting point to see if they are in fact the same compound. Upon mixing the two samples, if they are the same material, the melting point will be the same. If they are different, the melting point will be depressed since each will act as an "impurity" for the other. The boiling point of a liquid is the the temperature at which the liquid form of the compound becomes a gas. Boiling point is formally defined as the temperature at which the vapor pressure of the liquid is in equilibrium with the pressure at the surface of the liquid. Boiling point can sometimes be used to determine the purity of substances since pure substances have distinct boiling points. In the second part of the experiment, heating was stopped when continuous stream of bubbles appeared in the liquid sample. When this stream of bubbles ceased, the liquid will enter the CHEM31.1 Organic Chemistry

capillary tube. The moment the liquid enters the capillary corresponds to the boiling point of the liquid. During the initial heating, the air trapped in the capillary tube expands and leaves the tube. At the same time, vapour from the liquid also enters the tube. There is always vapour in equilibrium with a heated liquid. This gives rise to the initial stream of bubbles. Upon reaching the boiling point, the vapour pressure inside the capillary tube equals the atmospheric pressure. As the temperature rises just above the boiling point then the vapour will start to escape: the second set of bubbles. Once the heating is stopped, the only vapour left in the capillary comes from the heated liquid sealing its open end. When the liquid cools, its vapour pressure also decreases and when the vapour pressure drops just below atmospheric pressure, the liquid will be drawn into the capillary tube (forced there by the higher atmospheric pressure). The obtained boiling point of hexane from the experiment was 64 C. It was close to the theoretical boiling point of hexane which is 69 C. Theoretically, the boiling point of the distillate acquired from fractional distillation must be lower than the boiling point of the distillate obtained from simple distillation. The distillate from fractional distillation contains a higher percentage of ethanol since fractional distillation is more efficient than simple distillation. Ethanol serves as an impurity in water. Since ethanol is a volatile compound, it is easily vaporized. Thus, it has a low boiling point, lower than that of water. Since its boiling point is lower than water, it will decrease the boiling point of the substance. Consequently, if the boiling point of the impurity is higher than that of the pure compound, then the boiling point will increase. VII. Conclusion and Recommendations We can conclude that melting point and boiling point can be useful in product characterization and purity determination. If the melting point is known of the pure substance, then you can measure the melting point of the sample you have and then compare. If the melting point or boiling point is the same, then it is a good indication that the compound you have is the same as the pure substance and is pure. In terms of melting point determination, impure compounds melt over a lower yet wider range of temperatures than pure compounds. At the same time, boiling points of pure compounds are expected to be higher compared to the impure ones. Boiling points of organic compounds are lower than inorganic compounds because of their weaker interactions. The experiments highly recommend extra care with using the oil bath since they had a Page 3 of 4

difficulty in not breaking glass wares. It is also recommended that the thermometer to be used should have more than 100C so as to avoid repeating some procedures. VIII. References Bruice, Paula Yurkanis. Organic Chemistry 4th Edition. 81 88. (Prentice Hall, 2004) Organic Laboratory Technique 5: Boiling Point Determination. University of Calgary, Faculty of Science, Department of Chemistry. August 25, 2011. <http://www.chem.ucalgary.ca/courses/351/laborato ry/boilingpoint.pdf> Separation Techniques Revision PDF. Slideshare. August 25, 2011. <http://www.slideshare.net/missingisland/separation -techniques-revision-pdf> Experiment 4: MELTING POINTS OF ORGANIC COMPOUNDS. OChemOnline. <http://ochemonline.pbworks.com/f/04_mp.pdf>

I hereby certify that I have given substantial contribution to this report.

Capistrano, Kathrine Grace

Delos Santos, Windale Anne

Hurna, Ehcel

CHEM31.1 Organic Chemistry

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