Lab 1: Determining Melting Point and Evaporation Rates in Order to Identify Unknown Organic Compounds

Mimi Taskier Organic Chemistry 310, Section 005 Lab Partner: Robyn Jordan TA: Kristen Bert 9.20.2012

Introduction:
Melting and boiling points are two of the several characteristic physical properties of organic compounds. Pure solids will melt within a short range of the melting point temperature and knowledge of compounds boiling point coupled with its melting point help identify the purity of the compounds or new organic substances (1). The volatility of these compounds is directly related to the melting point and boiling points in that they characterize how likely individual molecules within a pure substance will dissociate. All organic moleculesand inorganic molecules for that matterare subject to intermolecular forces, the attractive and repulsive force which act between molecules. The more intermolecular forces present, the more difficult the molecule will be to break apart and will require more energy to achieve a phase change from solid to liquid (melting) or liquid to gas (boiling) to a more energetic state. The purpose of this experiment is to observe the evaporation rates and melting points of several unknown organic compounds and relate these observations to the known physical properties and identities of the given compounds. Organic chemists use their knowledge of the relationships between molecular structure, intermolecular forces, and the corresponding physical properties to predict behavior of these compounds and use them for further study. Without knowledge of the properties of the compound, experimental design could be compromised or compounds could be misused in the laboratory. In this experiment, those relationships between melting point, boiling point and the molecular structures are examined and clarified. This experiment was performed in two parts. Part I examined the evaporation rates of unknown compounds A and B as they were placed on individual watch glasses in equal quantities (6 drops). The rate of evaporation was measured and three separate trials were recorded. In part II of the experiment, unknown compounds C and D (solid crystals at 25C), were place into individual capillary test tubes in approximately equal amounts and inserted into a melting point apparatus with rapid heating and cooling capacity. The melting point apparatus immersed the entire capillary tube in heat allowing for uniform heating and was adjusted to gradually raise temperature by

approximately 1C per minute. A magnifying glass attached to the apparatus allowed the capillary tubes to be observed as the first drops of liquid are present (start melting point) and as the last portion of solid disappears into the liquid (1). The apparatus was connected to a digital reading device that displayed the changing temperature on PC application. Two trials examining melting starting and end points for unknown compounds C and D were performed.

Results:
Structures- These are the four given structures of unknown compounds A, B, C, and D. Figure 1: Naphthalene Figure 2: Phenol

Figure 3: Ethanol

Figure 4: Diethyl Ether

Data Table 1. Evaporation Periods of Unknown Compounds A and B

Unknown A B Trial 1 (s) 20.6 439.0 Trial 2 (s) 36.0 456.4 Trial 3 (s) 33.0 489.5 Average (s) 29.9 461.6

Table 1 displays the average times of evaporation for unknown compounds A and B with compound B yielding a higher average evaporation time at room temperature (25C).

Table 2. Melting Temperatures of Unknown Compounds C and D from Melting Point (MP) Apparatus
Unknown Trial 1 Start Melting Point (C) 81.6 38.7 Trial 1 Final Melting Point (C) 85.9 48.9 Trial 2 Start Melting Point (C) 81.5 38.7 Trial 2 Final Melting Point (C) 83.5 47.5 Average Start Melting Point (C) 81.6 38.7 Average Final Melting Point (C) 84.7 48.2 Avg. Melting Point Range (C) 81.6- 84.7 38.7- 48.2

C D

Table 2 shows two different melting temperaturesthe starting temperature at which the compound began to change from the solid to liquid state and the final temperature at which the

compound appeared completely melted. Two trials for each compound are displayed, an average of the trials, and the melting point range. The data shows the average melting point range for compound D is lower than compound C.

Table 3. Identified Unknown Compounds by Experimental Determination

Unknown A B C D Identity of Compound Diethyl Ether Ethanol Naphthalene Phenol

Table 3 displays the four unknowns and possible compounds that correspond to properties and experimentally determined melting and boiling points. The strategy for matching unknown compounds to known compounds is explained in the discussion.

Sample Calculations
Calculating Average Evaporation Period and Average Melting Temperatures: Average = [n1 + n2 + n3]/# of trials Unknown A [20.6 seconds + 36.0 seconds + 33.0 seconds]/3 = 29.9 seconds Average Final Melting Point for Unknown C [85.9C + 83.5C]/2 = 84.7C Calculating Percent Error of Experimentally Determined Melting and Boiling Points: Average Midpoint Melting Point = [Average Starting MP + Average Final MP]/2 % error = [observed actual]/actual x 100 Unknown C [81.6 + 84.7]/2 = 83.2C [83.2C 80.2C]/80.2C = 3.75% error

Discussion:
The application of the molecular structures and identity of the unknowns based on the experimentally determined melting and boiling points can be broken into two categoriesthe compounds that were liquids at 25C (unknowns A and B) and the compounds that were crystal solids at 25C (unknowns C and D). Between the two liquid compounds, the compound with the higher boiling point should have stronger intermolecular forces. In this experiment evaporation is synonymous with boiling point in that the boiling point is defined as the temperature at which the vapor pressure of the liquid exactly equals the pressure of the atmosphere exerted on it, approximately 760 mmHg in this experiment (1). If vapor pressure is high within a system, then the tendency of particles to escape from the liquid to gas phase is also high (a volatile compound), inferring a relative weakness in the intermolecular forces. Based on this principle, the liquid in this experiment with the stronger intermolecular forces should have a longer evaporation timethe time it takes for intermolecular forces to be

broken and for particles to reach the gas phase which is less ordered and a higher energy state. Melting point is defined as the temperature at which a substance changes from a solid to liquid state and the kinetic energy required per unit of particle to overcome intermolecular forces that order the molecules into a lower energy phase. The solid unknown compound with the strongest intermolecular forces should have the highest melting point. By examining the structures of the given compounds and identifying the intermolecular forces such as dipole-dipole attraction, van der Waals forces, hydrogen bonds, and ionic attraction can be identified based, the relative strength of the intermolecular forces within each compound can be ranked. Ethanol (C2H6O) has the smallest structure of all of the given molecules (2). Considering that is only contains two carbons, it should have relatively weak van der Waals forces because the strength of the van der Waals attractions increase with the increasing size of the molecule. Despite the weak van der Waals forces, ethanol is polar and can form hydrogen bonds between the hydrogen of the hydroxyl group on one molecule and the lone pair of electrons on the oxygen of a nearby molecule. Diethyl ether (C4H10O) is a relatively small organic molecule with only 4 carbons indicating weaker van der Waals forces because it is a small molecule (3). The molecule has no clear dipole, yet there is a partial negative charge on the central oxygen that forms the ether. Phenol (C6H5OH) is a comparatively larger molecule containing a benzene ring with an attached hydroxyl group (4). Due to its larger size, the van der Waals forces should be relatively stronger. Phenol can undergo hydrogen bonding due to the hydroxyl group and has strong dipole-dipole interactions from the lone pair of electrons on the oxygen. Additionally, the molecule is more stabilized due to the delocalized electrons around the benzene ring that is established by the alternating double bond (sp2 hybridization). Naphthalene (C10H8) has comparatively strong intermolecular forces at work (5). While it does not have any hydrogen bonding or apparent polarity, it has 10 carbon atoms, 4 more than phenol, and two adjacent benzene rings. The double ring structure gives naphthalene a geometry of overlapping sp2 orbitals which lock it very tightly into place, allowing for no

free rotation and close packing. This geometry and the delocalization of electrons across the alternating double bonds gives it stability and likely the highest melting point. Comparing the relative combination and strength of the intermolecular forces discussed above, diethyl ether and ethanol with the weakest forces are most likely liquids at 25C (unknowns A and B). Because ethanol has hydrogen bonding from the hydroxyl group, which is one of the strongest intermolecular forces, it will have a longer evaporation time. Unknown A had an average experimental evaporation time of 29.9 seconds and unknown B had an average experimental evaporation time of 461.6 seconds (Table 1). Given the greater evaporation time for unknown B, its identity, based on the experimental results, must be ethanol. Deductively, unknown A must be diethyl ether. The remaining two compounds, phenol and naphthalene, are solids at 25C (unknowns C and D). Because naphthalene has a double ring structure with a tightly packed geometric structure compared to the single benzene ring structure with a hydroxyl group on phenol, it has stronger intermolecular forces and will have the higher melting point. Unknown C had an average melting point range of 81.6- 84.7C (Table 2). Unknown D had a lower average melting point range of 38.7- 48.2C (Table 2). Given the higher melting point for unknown C, its identity, based on the experimental results, must be naphthalene. Deductively, unknown D must be phenol. The actual melting and boiling points for the given compounds supports the experimental results of the unknown substances and the analysis of the molecular structures. Diethyl ether has an actual boiling point of 34.6C and a melting point at 116.3C affirming that it would be a liquid at 25C and the first compound to quickly evaporate therefore matching the identity as unknown A (3). Ethanol has a actual boiling point of 78.5C and a melting point of -114.1C supporting that it would also be a liquid at 25C and would have the second faster evaporation rate (2). These properties match the identity of unknown B. Naphthalene has an actual boiling point of 218C and a melting point of 80.2C which affirms that is a solid at 25C with the highest melting point, matching unknown compound C (5). Finally, phenol has an actual boiling point of 182C and a melting point of 42C matching the properties of unknown D.

The experimental values of melting and boiling points of the four compounds do not exactly match the actual values given for compounds suggesting experimental error. During this experiment there were significant sources of systematic and random error. In Part I of the experiment, the watch glasses used for unknown compounds A and B were different in size and one of the watch glasses had ridges which increased pooling of the liquid and decreased the surface area. Lower surface area for the liquid would have decreased the rate of evaporation because fewer liquid particles would have come into contact with the vapor. Additionally, during measurement the experimenter varied the time at which the evaporation period began. For one trial the period began right before the sixth drop was added. This may have resulted in a systematic error that could affect the accuracy of the evaporation rate. During Part II of the experiment there were a series of possible errors. The use of the capillary tubes in the melting point apparatus did not ensure consistent measurements of crystal solid that was melted across all trials. Using tubes of that miniature size made it difficult to make uniform samples. Another random error was the limit of two trials for each unknown. There may be imprecision in the data due to the small number of trials conducted. In between trials, the melting point apparatus was not brought down completely to a low temperature disallowing standardization of the trial procedures for each unknown trial. Additionally, different experimenters viewed the melting start and end points for different trials contributing systematic error in the lack of consistency in qualitative observation. Finally, the most significant systematic error in this experiment was the quality of unknown D at the time the experiment was performed. While unknown D should be a crystalline solid, it was beginning to melt at 25C producing an oily liquid while being inserted into the capillary tubes. The state of the compound suggests that it was likely contaminated prior to the experiment, effectively lowering the melting point. The percent error of the experimental melting point for compound D (phenol) was 3.57%. Comparatively compound C (naphthalene) produced a similar percent error of 3.75%. Conclusively, the data would be overall improved if compound D had not been contaminated, if more trials had been performed for each compound, and if a

standardized measurement procedure had been implemented to minimize systematic error.

References:
(1) Williamson, K.L. Macroscale and Microscale Organic Experiments, 6th ed.; HoughtonMifflin: Boston, 2011. (2) Ethyl Alcohol, Material Safety Data Sheet. Science Lab. http://www.sciencelab.com/msds.php?msdsId=9923956 (accessed Sept 17, 2012). (3) Ethyl Ether, Material Safety Data Sheet. Science Lab. http://www.sciencelab.com/msds.php?msdsId=9927164 (accessed Sept 17, 2012). (4) Phenol, Material Safety Data Sheet. Science Lab. http://www.sciencelab.com/msds.php?msdsId=9926463 (accessed Sept 17, 2012). (5) Naphthalene, Material Safety Data Sheet. Science Lab. http://www.sciencelab.com/msds.php?msdsId=9927671 (accessed Sept 17, 2012).