Experiment 5: Boiling Point and Melting Point Determination Cailao, Ma. Victoria T. Masigan, Maureen Margaret R.

Group 5, Chem 31.1, AB2, Ms. Denise Arganda April 30, 2009 I. Abstract Two of the more important physical properties of pure substances are the boiling point and the melting point. They can be used to characterize organic and inorganic substances and are also an indicative of the purity of a substance. The boiling point of a liquid is the temperature at which that liquid is converted to a gaseous state. It 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 melting point is the temperature at which a solid is converted to liquid. In this experiment, melting and boiling points were determined by conducting a setup consisting of capillary tubes, thermometer, and oil bath. II. Keywords: boiling point, melting point, benzoic acid, urea, hexane, distillate III. Introduction The melting point of a substance is the temperature at which the solid phase converts to the Boiling point refers to the temperature at liquid phase in less than 1 atmosphere of pressure. which the vapor pressure of a liquid slightly The melting point is one physical property of a exceeds the pressure of the atmosphere above the substance that is useful for characterizing (describing) liquid. At temperatures below the boiling point and identifying the substance. To measure the (b.p.), evaporation takes place only from the melting point of a substance, it is necessary to surface of the liquid; during boiling, vapor forms gradually heat a small sample of the substance while within the body of the liquid; and as the vapor monitoring its temperature with a thermometer. The bubbles rise through the liquid, they cause the temperature at which it begins to liquify is the lowest turbulence and seething associated with boiling. If end of the melting point range and the temperature at the liquid is a single substance or an azeotropic which the last solid disappears is the highest end. A solution (a mixture that has a constant b.p.), it will pure substance normally has a melting point range no continue to boil as heat is added without any rise in larger than 1-1.5 C. temperature; that is, boiling occurs at constant Although many substances melted, temperature regardless of the amount of heat crystallized, and melted again repeatedly without applied to the liquid. chemical decomposition, others chemically When the pressure on a liquid is increased, decompose before they melt, forming substances of the b.p. goes up. Water at 1 atmosphere pressure lower molecular weight. The temperature of (760 torr, or about 14.7 lb/sq in) boils at 100 C decomposition is just as useful as the melting point in (212 F), but when the pressure is 218 physically characterizing a substance. Decomposition atmospheres (165,000 torr, or 3200 lb/sq in), the is usually signaled by a color change; for example, b.p. reaches its maximum, 374 C (705 F). Above white substances invariably start to turn brown near this temperature (the critical temperature of water), the decomposition temperature. The temperature, at liquid water is identical to saturated steam. which the color change is first observed, signals that If the pressure on a liquid is reduced, the the substance is approaching the decomposition b.p. is lowered. At higher elevations, where air temperature. At a higher temperature, liquid may pressure is less, water boils below 100 C. In form. At this temperature or at an even higher Denver, Colorado, which is 1.6 km (1 mi) above sea temperature, gas bubbles may be seen if gaseous level, the b.p. of water averages 94 C (201 F). decomposition products are formed. All of these When the pressure on a sample of water falls to temperatures aid in characterizing a substance, so all 4.55 torr (0.088 lb/sq in), boiling occurs at 0 C (32 should be noted and reported. F), which is the normal freezing point. The objectives of the experiment are the Boiling points cover a wide temperature determination of the melting point of benzoic acid and range. The lowest b.p. is that of helium, -268.9 C (benzoic acid-urea mixture; and the boiling point of 452 F). The highest is probably that of tungsten, hexane and the distillates. It also aims to teach about 5900 C (10,650 F). The boiling points given students the proper laboratory techniques in in the separate articles on the various elements and determining the said physical properties. compounds apply at normal pressure unless specifically stated otherwise.

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IV. Experimental A. Melting Point Determination of Benzoic Acid and Benzoic Acid-Urea Mixture Two capillaries (1 mm in diameter and 6 cm in length) were prepared, one end of each capillary sealed. Approximately 0.5 g benzoic acid was obtained and powdered using mortar and pestle. The powdered sample was introduced into the first capillary tube until it occupied about 1 cm in height. This was done by pushing the open end of the capillary into the powder and tapping the closed end on the table top. Another 0.5 g of benzoic acid was obtained; a pinch of urea added to the sample. The mixture was powdered using mortar and pestle, and then introduced to the second capillary tube. The two capillaries were attached to the thermometer.

Figure 2: Boiling Point Apparatus

The capillary tube was introduced into the test tube with the open end immersed in the liquid sample. The temperature of the oil bath was raised until a rapid and continuous stream of bubbles was observed. The flame was removed and the bath was allowed to cool. The temperature reading was taken as the instant bubbles ceased to come out of the capillary tube and just before the liquid sample enters the capillary tube. The respective boiling points of the two distillates (obtained in Experiment #4) were determined using the same procedure. V. Results A. Melting Point Determination Sample Benzoic Acid Benzoic AcidUrea Mixture
Figure 1: Melting Point Apparatus

Melting Point Range ( ) Experimental Theoretical 115 121-122 85 --

Table 1. Experimental and Theoretical Melting Points of the Samples Used

10 mL of cooking oil was introduced in a 20-mL test tube. The thermometer, along with the capillaries, were immersed in the oil bath and heated over a hot plate. The temperature at which the sample starts to liquefy and the temperature at which the solid has completely liquefied were recorded. B. Boiling Point Determination of Distillate and Hexane Three capillaries were prepared, one end of each capillary sealed. 10 drops of hexane was introduced into the 5-mL test tube. Attach this to the thermometer as shown in the figure below.

B. Boiling Point Determination Sample Hexane Distillate 1 (from simple distillation) Distillate 2 (from fractional distillation) Boiling Point ( ) Experimental Theoretical 68 82 105 69 78.3 78.15

Table 2. Experimental and Theoretical Boiling Points of the Samples Utilized

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VI. Discussion Boiling Point The boiling point of a compound is the temperature at which it changes from a liquid to a gas. This is a physical property often used to identify substances or to check the purity of the compound. It is difficult, though, to find a boiling point. Usually, chemists can only obtain a boiling range of a 2 - 3C accuracy. This is usually sufficient for most uses of the boiling point. A liquid boiling point is the temperature when its vapor pressure is equal to the atmospheric pressure. Normally, the boiling point is measured at one atmosphere (101 kPa or 760 mmHg or 760 torr). Like melting points, boiling points are characteristic properties of pure materials. Boiling points are approximately related to their molecular weight, the higher the molecular weight, the higher the boiling point. Boiling point is the temperature at which the vapor pressure of the liquid exactly equals the pressure exerted on it, causing the liquid to "boil" or change to the gas phase. For purposes of this laboratory experiment, the boiling point of an organic liquid is the temperature range over which the state of the organic compound changes from the liquid phase to the gas phase at 760mm of pressure. While the boiling point is a characteristic physical property of a compound, many compounds may have the same boiling point. The molecules of compounds that exist in the liquid state are relatively close together, compared with molecules of gaseous compounds. The close proximity of molecules in the liquid state allow these molecules to interact via non-covalent interactions (dipole-dipole, H-bonding, van der Waals forces). In general, these interactions are favorable and help to hold the molecules together in a defined volume, but still allow free motion or "flow". Conversely, molecules of a gaseous compound are much farther away from each other and are not confined to a specific volume by noncovalent interactions. If enough energy (often in the form of heat) is provided to the liquid, the molecules begin to move away from each other by "breaking" the non-covalent forces that hold the compound in the liquid state. Structural features of a compound influence the boiling point by increasing or decreasing the molecules' ability to establish and maintain noncovalent interactions that hold the molecules close together in the liquid state. The structural features of a compound that influence boiling point are: (a) Polarity - Increased H-bonds, polar covalent bonds or formal charges in a molecule tend to increase the boiling point. More polar elements in a
Chem 31.1 Boiling Point and Melting Point Determination

molecule increase the total number of dipole-dipole, ion-dipole and/or H-bonding interactions. More energy (higher boiling point temperature) is necessary to break these interactions and allow the molecules to move away from each other into a gaseous state. (b) Molecular Weight - Increased molecular weight increases boiling point. A higher molecular weight compound has more atoms that can be involved in non-covalent interactions. The greater the number of non-covalent interactions, the more energy (higher boiling point temperature) that is necessary to break the non-covalent interactions to transform the compound from the liquid phase to the gas phase. (c) Branching - Branching decreases boiling point. It blocks molecules from packing together too closely. The closer molecules are, the stronger the noncovalent interactions. Thus, molecules that are forced to be farther away from each other due to branching have weaker non-covalent interactions. Less energy (lower temperatures) is needed to induce a phase change from the liquid phase to the gas for branched compounds relative to straight chain compounds. Melting Point The melting point of a crystalline compound is best defined as the temperature at which the solid phase is in equilibrium with the liquid phase. At the melting point, sufficient heat has been applied so that thermal vibrations of the molecules in the crystal lattice are great enough to overcome the electrostatic, dipole, and van der Waals cohesive forces, allowing the molecules to take on the more random and mobile arrangement of the liquid state. The freezing point, or the temperature observed as the liquid form cools and solidifies, is the same temperature as the melting point. Melting points are readily obtained with great precision using simple apparatus. It is the most widely determined and useful physical constants of organic compounds. Melting points are used both as criteria of purity and as a clue to the identification of organic compounds. A narrow melting point range is indicative of a pure substance. It is a good generalization that, as a compound is purified, the melting points become sharper (range narrower) and higher. Since hundreds of organic compounds may have similar melting points, exact identities are difficult and risky, based only on simple melting point determinations; but at least the number of possibilities can be narrowed from the millions of known organic compounds. Observed melting points are generally recorded as a range of temperatures because of the rather large quantities of compounds used and the difficulty in controlling the experimental variables in the usual methods for determining melting points.
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Only when one or two crystals of an extremely pure compound are melted on specially controlled hot stages and observations conducted with the aid of high-powered magnifiers and/or polarized light are then, melting points observed as single temperatures. The temperatures recorded as the observed melting point range are the temperature at which there is a definite sign of liquid in the sample and the temperature at which there is nothing but liquid in the sample, e.g. 123.5-125.0 C. An apparent shrinking, slumping, or softening is often the first indication that something is about to happen as the melting point is approached but these changes should not be mistaken for the first signs of liquid in the sample. The melting point range (the interval between the beginning of liquefaction and complete liquefaction) is a valuable inaction of the purity of the substance. A pure crystalline organic compound generally possesses a sharp melting point range, usually 2.The melting point range is influenced not merely by the purity of the material but also by factors such as the size of the crystals, the amount of material, rate of heating, determination method, experimenter, etc. In the most common methods of melting point determination, a small amount of finely powdered crystals is placed in a thin-walled capillary tube. The tube is placed in very close proximity to a thermometer and the capillary tube is heated in a small electric block or oven or in a wellstirred oil bath. A finite time is necessary for the transfer of heat from the hot block or bath through the walls of the capillary tube and throughout the mass of the sample. If the block or bath is heated too rapidly, the temperature of the block or bath will rise several degrees. This time lag required for the melting process makes the observed melting point range larger than the theoretical one. Likewise, too rapid heating will cause the thermometer reading to be lower than the actual block or bath temperature, because of the time required for heat transfer to the mercury. Consequently, the observed melting point range will generally be broader and lower than the actual melting point range if too rapid heating occurs. Satisfactory results are obtainable if a uniform rate of heating of no more than 1 or 2 rise per minute is employed in the vicinity of the melting point. The temperature may normally be raised rapidly until 10 or 15 below the melting point with the rate of heating then being adjusted to the uniform rise of 1 to 2 per minute. To minimize the lag in the melting process and heat transfer the compound should be finely ground and packed densely to a height of 2-5 mm in a fine capillary tube having a small diameter and very thin walls. Two other sources of error in
Chem 31.1 Boiling Point and Melting Point Determination

melting point determinations are incorrect calibration of the thermometer scale (this can be eliminated by standardizing the thermometer with a set of melting point standards) and stem exposure of the thermometer. The surrounding atmosphere cools that portion of the mercury column that is exposed above the surface of the heating bath of block. The registered temperature is, therefore, below the true temperature of the mercury in the bulb of the thermometer and of the sample in the capillary tube. For temperatures below 100 C, this cooling effect does not cause any considerable error, but for high temperatures the observed reading maybe several degrees lower than the true temperature. Systematic variations of melting point with changes in structure are not as obvious or predictable as are the variations in boiling point. (a) Molecular Weight - Although melting points do generally increase with increasing molecular weight, the first members of homologous series (compounds differing by only a CH2) often have melting points that are considerably different from what would be expected on the basis of the behavior of the higher homology In some homologous series of straightchain aliphatic compounds, melting points alternate: the melting point of successive members of the series is higher or lower than that of the previous member, depending on whether the number of carbon atoms is even or odd. Sometimes, as with the normal alkanes, the melting points of successive members of the series always increase, but by a larger or smaller amount, depending upon whether the number of carbons is even or odd. (b) Polarity - As with boiling points, compounds with polar functional groups generally have higher melting points than compounds with nonpolar functional groups. (c) Branching - In contrast to the case with boiling points, highly branched or cyclic molecules (relatively symmetrical molecules) tend to have higher melting points than their straight-chain isomers. The combined effects of branching or the presence of rings, then, are to reduce the range of temperature over which the liquid can exist at a vapor pressure of less than 760 torr. In extreme cases, a liquid range does not exist at a vapor pressure of less than 760 torr; at atmospheric pressure, the substance will sublime without melting. Hexachloroethane and perfluoro-cyclohexane behave in this way. Melting points of organic compounds are usually markedly influenced by the presence of even small amounts of miscible or even partially miscible impurities. These impurities normally depress the
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melting point and broaden the range. This lowering and broadening of the melting point range is presumably caused by the molecules of the impurity interrupting and weakening the uniform structure of the crystal lattice of the organic compound. These facts may be used to establish the identity of organic compounds by determining the melting points or mixtures, a method commonly referred to as mixed melting points. Mixed Melting Points Two sample of the same compound, having the same melting point separately, should have the same melting point when they are mixed together. Also, in general, sample of two different compounds having the same or similar melting points separately, will act towards each other as impurities when they are mixed together; hence, such mixtures will have broadened and depressed melting point ranges. Identification of a solid unknown by mixed melting points is remarkably reliable when an authentic specimen is available. A broadened melting point range may be due not only to impurities present in the original sample but also may result from the pure substance undergoing some decomposition before or during the melting. In some instances the material undergoes a slight softening or contraction (sintering) at a temperature below the true melting point; in others, the material may become discolored slightly; and in still others, the substance may decompose completely and turn black so that a definite melting point cannot be ascertained. The behavior of substance on melting should be observed closely and recorded in the lab-book. Each time a melting point is determined or rechecked a fresh sample should be placed in a new capillary since even slight, undetected decomposition may cause a false reading if the old sample is melted again. Broadened and depressed melting point ranges are also frequently obtained if the sample is not completely dry. It is because the sample is wet with water or some other solvent used in the purification of the compound. Instead of melting, wet compounds merely dissolve in the solvent present as heat is applied. If the compound dances around or there are bubbles when melting, a wet compound should be suspected. Experimentally observed melting points will normally match literature melting points within two degrees, with the observed melting points generally on the low side since literature melting points as a rule are reported on compounds of very high purity. Variations in literature melting points from one reference to another for the same compound are encountered frequently. It is due to differences in purity of the samples.

VII. Guide Questions and Answers 1. Give an explanation of the observed boiling points. The benzoic acid-urea mixture has a melting point range lower and larger in the range of values than the benzoic acid alone. This is brought about by the impurity of the mixture. Impurities change the crystal lattice of a pure compound, making it asymmetrical or poorly organized. Since melting point is dependent on the high symmetry and organization of molecular structures, any change on the latter will cause the deviation of the former. 2. Give an explanation of the observed boiling points of the two distillates. Whatever method of preparation is used, the ethanol is initially obtained in admixture with water. Although the boiling point of ethanol, 78.3C, is significantly lower than the boiling point of water, 100 C, these materials cannot be separated completely by distillation. Instead, an azeotropic mixture (i.e. a mixture of 95% ethanol and 5% water) is obtained, and the boiling point of the azeotrope is 78.15C. In a distillation, the most volatile material (i.e. the material that has the lowest boiling point) is the first material to distill from the distillation flask, and this material is the azeotrope of 95% ethanol which has the lowest boiling point. If an efficient fractionating column is used, there is obtained first 95% alcohol, then a small intermediate fraction of lower concentration, and then water. But no matter how efficient the fractionating column used, 95% alcohol cannot be further concentrated by distillation. The separation of a mixture by fractional distillation occurs because the vapour has a different composition from the liquid from which it distils (i.e. the vapour is richer in the more volatile component). We cannot separate 95% alcohol into its components by distillation, because here the vapour has exactly the same composition as the liquid; towards distillation, then, 95% alcohol behaves exactly like a pure compound. 3. What effect would poor circulation of the melting point bath liquid have on the observed melting point? Poor circulation can cause uneven heating of a sample. This may lead to inaccurate results. Observed melting point may be unusually higher than the actual.

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4. What effect would the incomplete drying of a sample have on the melting point? Incomplete drying of a sample may cause some depression of the melting point. This is caused by the impurities that are left in the sample. Any impurity of a substance lowers its melting point. 5. Three test tubes, labeled A, B, and C, contain substances with approximately the same melting points. How could you prove the test tubes contain three different compounds? First, determine the respective melting points of the unknown compounds. If they are approximately the same, mix the substances in test tubes A, B, and C. Determine the melting point exhibited once again. If the melting point of the mixture depresses from the individual melting points of the substances, therefore, the unknown compounds are different. 6. Which would be expected to have a higher boiling point t-butyl alcohol or n-butyl alcohol? Explain. n-butyl alcohol is expected to have a higher boiling point than t-butyl alcohol because the previous has a more linear structure compared to tert-butyl alcohol which exhibits branching. This decreases the strength of the intermolecular forces, thus, also reduces the boiling point. 7. Calculate the vapor pressure of a solution containing 30mol % hexane and 70mol % octane at 90C assuming Raoults Law is obeyed. (Given: vapor pressure of the pure compounds at C: hexane=1330 torr; octane=253 torr). Phexane=PhexaneXhexane = (1330 torr)(0.3) = 399 torr Poctane=PoctaneXoctane = (253 torr)(0.7) = 177.1 torr Ptotal=Phexane + Poctane =399 + 177.1 = 576.1 torr VIII. Conclusion and Recommendations A simple and widely used method for determining the identity of an unknown liquid is by measuring the temperature at which it boils. This temperature, called the boiling point, is a physical property. It can be used to identify liquids much like

solids can be identified by melting points. The apparatus to be used is a simple distillation set-up. The normal melting point of a solid is defined as the temperature at which the solid and liquid are in equilibrium at a total pressure of 1 atmosphere. In contrast to the volume change that accompanies the vaporization of a liquid, the change in volume that takes place upon the melting of a solid is very small. This makes the melting point of a solid, unlike the boiling point of a liquid, practically independent of any ordinary pressure change. Since the melting point of a solid can be easily and accurately determined with small amounts of material, it is the physical property that has most often been used for the identification and characterization of solids. A dilute solution of a liquid begins to freeze at a temperature somewhat lower than the freezing point of the pure liquid. The presence of an impurity causes a reduction of the freezing point of the sample. As the pure solvent crystallizes from solution, the concentration of the impurity must increase and the freezing point of the solution must fall. Thus, a sharp melting point (actually, a melting range of less than about 1C) is often taken as evidence that the sample is fairly pure, and a wide melting range is evidence that it is not pure. If two samples have different melting points, their molecules must differ either in structure or in configuration. They must be either structural isomers or diastereomers. If the melting points of two samples are the same, the structures of their molecules must be the same, although they might have enantiomeric configurations. These statements apply only to pure substances, and do not take into account the fact that some substances can exist in different crystalline forms that have different melting points. Mixtures of different substances generally melt over a range of temperatures, and melting is usually complete at a temperature that is below the melting point of at least one of the components. Thus, the nonidentity of two substances of the same melting point can often be established by determining that the melting point of a mixtures of the two is depressed. If each individual sample melts "sharply" (and at the same temperature, of course), and if an intimate mixture of the two, made by rubbing approximately equal amounts together, melts over a wide range, the two substances are not the same. Usually, however, in establishing the identity rather than the nonidentity of two samples, it is unfortunate that the converse is not always true: the absence of a depression of the melting point or of a wide melting range of the mixture is not certain evidence that the two substances are identical in molecular structure and configuration. Boiling a liquid and melting a solid involve the same process that is, breaking away from the attractive forces that hold particles together. Thus, the
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Chem 31.1 Boiling Point and Melting Point Determination

strength of the interparticle forces of attraction (IPFA) is the principal factor that determines boiling point and melting point. Moreover, the factors affecting boiling point and melting point are: molecular size, branching, polarity, molecular symmetry and intramolecular H-bonding. IX. References Brown, T. L., Lemay Jr., H. E., Bursten, B. E. Chemistry: The Central Science (9th ed.). Singapore: Pearson Education (Asia) Pte Ltd. Committee on General Chemistry (2006). Laboratory manual in general chemistry (2006 ed.). Manila, Philippines: University of the Philippines Manila Microsoft Encarta 2007. 1993-2006 Microsoft Corporation. All rights reserved. Sackheim, G. I, Lehman, D,D. (2002) Chemistry for the Health Sciences (8th ed.) Upper Saddle River, New Jersey: Pearson Education Asia Pte. Ltd. Whitten, K. W, Davis, R. E, Peck, M. L, (2005) General Chemistry (7th ed.). Singapore: Thompson Learning Asia Pte. Ltd.

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

Cailao, Ma. Victoria T.

Masigan, Maureen Margaret R.

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