EXERCISE 1 MOLECULAR WEIGHT DETERMINATION BY VAPOR-DENSITY METHOD

Performed by: Legaspi, Anna Esperanza Q. Ayado, Vanessa Carla V. Casas, Maria Josefina S. Castillo, Immanuel Joy B. De Jesus, Cyrille P.

Date Performed: 27 November 2012 Date Submitted: 4 December 2012

Section 2L Submitted to: Mr. Edison G. Boongaling

I.

Introduction

Obtaining the molecular weight of a substance is helpful in determining the identity of that substance. There are numerous ways in achieving this and vary also in many ways for different substances. For volatile liquids, this can be done by utilizing vapour-density methods. Vapour density methods involve the vaporization of a volatile liquid to fill a known volume at a given pressure and temperature. Three of the most common of these methods are Dumas bulb method, Victor Meyer method, and temperature vapour-density method (TMVD). TMVD is the one used in this exercise. In the Dumas bulb method, the most of common of the three, the mass, temperature, volume, and the pressure of the vapour are obtained. This method uses a special container for the volatile liquid, called the Dumas bulb in which the liquid is vaporized upon heating. In this method, it is assumed that the vapour and the water bath have the same temperature and the pressure inside is equal to the atmospheric pressure. It also assumes that the disappearance of the Schlieren jet inside the bulb and the complete evaporation of the liquid are simultaneous. On the other hand, the Victor-Meyer method uses a more elaborate set-up, resulting to more precise results. Similarly, the mass and the volume of the substance at a given barometric pressure and known temperature are obtained in this method. Lastly, TMVD method is accomplished by following liquid vaporization from a thermocouple response versus time curve. Like the Dumas bulb method and the Victor-Meyer method, the mass, temperature, volume, and the pressure of the vapour are obtained. However, it uses a thermocouple to facilitate the direct measurement of the temperature of the vapour exactly after the complete evaporation of the liquid inside the flask. Thus, it solves some of the assumptions in the Dumas bulb method. In these methods, the molecular weight of the volatile liquid can be determined by the manipulation of the ideal gas equation. (1-1) where: P = pressure V = volume of the gas n = number of moles of the gas R = ideal gas constant (0.082056 L-atm/mol-K) T = temperature of the gas This state function can be used to determine the molecular mass by obtaining the variables- volume, temperature, pressure and amount of substance. Rearranging equation 1-1, the molecular mass can be obtained:

(1-2) However, the Ideal Gas Law is a limiting law that describes the behavior of a hypothetical substance which is the ideal gas. At ordinary pressure or temperature, the ideal gas equation is only approximately obeyed by the real gases. However, it is an exact description limit of zero gas pressure or density (Shoemaker, 2009). This experiment is aimed to illustrate one of the many applications of the ideal gas equation and to determine the approximate molecular weight of a volatile substance, specifically, acetone and methanol by TMVD method.

II.

Materials and Methods

Initially, the room temperature, barometric pressure and relative humidity were obtained. The samples used were Acetone (bp= 56C) and methanol (bp= 64 C), and for each sample, two trials were performed. A dry and empty 100-mL volumetric flask with Teflon plug was weighed at room temperature. The assembly was then pre-heated in a water bath until its temperature reaches 10C below the boiling point of the sample. Immediately after pre-heating, the mass of the volumetric flask was determined. A 0.25mL of the sample was then placed inside the flask and was returned in the Temperature-Moderated Vapor Density (TMVD) set-up.

The volumetric flask was continued to be heated until the thermocouple temperature was 5C below the boiling point of the sample. At this point, the temperature in the thermocouple was read and recorded continuously at 10-second intervals. The temperature reading was stopped at 2C above the samples boiling point. The volumetric flask was again weighed immediately and was recorded as the mass of the flask and vapor. To determine the inflection temperature (Ti), a plot of the thermocouple temperature-time response curve was prepared using the data obtained earlier. Lastly, the volume of the flask was determined by filling the flask with water and weighing it at room temperature.

III.

Results and Discussion

In this experiment, the molecular weight of acetone and methanol were obtained using temperature-monitored vapour density (TMVD) method. After obtaining the necessary data, the ideal gas equation was used to calculate the molecular weight of the samples. However, experiments show that real gases approach ideality when the pressure approaches zero (Castellan, 1983). Since the ideal gas equation is directly involved in the calculation of the molecular weights of the samples, some deviations from the results are expected to occur given that the conditions wherein the experiment was conducted was not in idealizing conditions. From equation 1-2, it can be seen that both the pressure and the volume are inversely proportional with the molecular weight. Thus, it is expected that any increase or decrease in both parameters will result to an opposing change in the molecular weight. On the contrary, the mass and the temperature of vapour being studied are directly proportional to its molecular weight. Therefore, an increase or decrease in value of these parameters during the experiment will cause a corresponding increase or decrease in the calculated molecular weight of the sample. To minimize these deviations, certain corrections should be made. Since the idealizing conditions involve low pressure and high temperatures (Atkins and de Paula, 2006), corrections should also me be made in these parameters. Proper techniques should also be observed so as to minimize any more deviations from the equation due to erroneous data. From the three most common vapour density methods, it is the TMVD that was used in the experiment. This is most likely because TMVD is most advantageous compared to the other two. In the Dumas bulb method, a special container for the volatile liquid, called the Dumas bulb is used. This is where the liquid is vaporized while it is heated. It is roughly almost the same as TMVD. However, it has certain assumptions that dont hold true at all times causing errors to happen more likely. It is assumed in this method that the vapour and the water bath have the same temperature and the pressure inside is equal to the atmospheric pressure. It also assumes that the disappearance of the Schlieren jet inside the bulb and the complete evaporation of the liquid are simultaneous. On the other hand, the Victor-Meyer method is liable to give more precise results. However, the downside of this method is it requires a more elaborate set-up. Like the Dumas bulb method and the Victor-Meyer method, the mass, temperature, volume, and the pressure of the vapour are obtained in TMVD. However, it uses a thermocouple to facilitate the direct measurement of the temperature of the vapour exactly after the complete evaporation of the liquid inside the flask. Thus, it solves some of the assumptions in the Dumas bulb method. At the start of the experiment, the room temperature, barometric pressure and the relative humidity in the laboratory were obtained. This would be used in the calculation for the molecular weight of the samples methanol and acetone. The masses of the dry and empty volumetric flask with Teflon plug at room temperature at different trials were also recorded. To obtain the weight of the flask when it is heated, the assembly (flask with Teflon plug) was heated to a temperature 10 C below the boiling point of the sample and then afterwards, weighed. It is assumed that the empty pre-heated flask also contained moist air inside. Thus, during calculations, the mass of the moist air was subtracted from the weight of the flask. If this was not done, the mass of the vapour that would be obtained in the calculations would decrease since the mass of the flask would be heavier. This would result to a lower calculated molecular weight. Afterwards, the sample was put in the flask and continued to be heated at 5 C below the boiling point of the sample. At this point, the temperature in the thermocouple was recorded at 10-second intervals until the temperature reached 2 C above the boiling point of the sample. The flask was again weighed. This was then plotted in temperature vs. time in minutes to be

able to determine the inflexion point of the sample. The sample graphs are shown in Figures 1.2 and 1.3. (Graphs for acetone are not available since all the data needed were given by the instructor.
68 67 Temperature (C) 66 65 64 63 62 61 60 0 5 10 15 20 25 30 35 Time (minutes)

Figure 1.2 The thermocouple temperature-time response curve of methanol (trial 1)

69 68 67

Temperature (C)

66 65 64 63 62 61 60 0 5 10 15 20 25

TIme (minutes)
Figure 1.3 The thermocouple temperature-time response curve of methanol (trial 2) This inflexion point was assumed to be the boiling point of the sample and was the one used to calculate the molecular weight of the vapour using the rearranged ideal gas equation. The volume of the flask was also obtained by filling it with water and then weighed. All the data mentioned above and other necessary data used for calculations are shown in tables 1.2 and 1.3. It is shown in part IV how the molecular weights of the samples were obtained using these

data. Additionally, the vapour pressure and density of water were obtained from other sources. The values are shown in Table 1.1 Table 1.1 Density and vapor pressure of liquid water Temperature( 25 26 27 28 29 30 31 32 33 34 35 ) Vapor pressure (mmHg) 23.8 25.2 26.7 28.3 30 31.8 33.7 35.7 37.7 39.9 42.2
th

Density(g/ml) 0.9970 0.9968 0.9965 0.9962 0.9959 0.9957 0.9954 0.9951 0.9948 0.9944 0.9941

Reference: CRC Handbook of Chemistry and Physics, 64 edition.,1983-4. Table 1.2 Obtained data for the determination of the molecular weight of Acetone Parameters Room Temperature (TR), Barometric Pressure (PB), mmHg Relative Humidity, % Mass of Volumetric flask at room temp( mFlask,Tr) , g Mass of Vol. Flask + H2O (mFlask+water), g Mass of pre-heated Volumetric Flask(mf), g Mass of volumetric flask +vapor (mflask+vapor) , g Inflection point ( ) Measurements Trial 1 29 749.02 70.5 69.6571 168.6919 69.6548 69.7521 53.4 Measurements Trial 2 29 746.338 70.5 67.1789 169.6889 69.1539 68.2569 53.8

Table 1.3 Derived data for determination of the weight of Methanol Parameters Room Temperature (TR), Barometric Pressure (PB), in Hg Relative Humidity, % Mass of Volumetric flask at room temp( mFlask,Tr) , g Mass of Vol. Flask + H2O (mFlask+water), g Mass of pre-heated Volumetric Flask(mf), g Measurements Trial 1 28 29.70 75 67.0043 166.604 66.9955 Measurements Trial 2 28 29.70 75 68.6367 169.7598 68.7045

Mass of volumetric flask +vapor (mflask+vapor) , g Inflection point ( )

67.0780 65.8

68.9217 65.8

Table 1.4 shows the comparison of the calculated values of each trial and the known values of the molecular weights of the samples. Table 1.4. Comparison of experimental value with literature value Molecular weight, g/mol Literature value* Acetone 58.07 Methanol 32.04 th *Merck Index. 12 edition Experimental value Trial 1 57.54 55.38 Trial 2 58.39 92.42 Percent error, % Trial 1 0.91 72.85 Trial 2 0.54 188.45

It can be seen that for acetone, the calculated values have smaller percent errors compared to the calculated values of methanol. Methanol was expected to have a higher percent error because it is more volatile compared to acetone. During the experiment, the vapour inside the flask might have escaped through the Teflon plug or while wiping the mouth of the flask. This would cause a lower measurement of the weight of the flask plus vapour, thus resulting to a lower mass of the vapour. Since the mass of the vapour is directly proportional to the molecular weight of the vapour, a decrease in vapour mass would also mean a decrease in molecular weight. However, the calculated values have higher molecular weights. This might be caused by wet volumetric flask used in the experiment. In addition, the mass of moist air subtracted from the mass of the vapour must have been lighter than the real mass of moist air, resulting to a heavier mass of the vapour and a heavier molecular weight. Other errors might have been caused by instrumental and human errors. The procedure of manually determining the inflexion temperature using the graph is one. Although there is a direct access of measuring the temperature inside the flask using the thermocouple, it was relatively difficult to pinpoint an accurate inflexion point in the graph, especially when the graph obtained is flawed. In the calculations, the vapour pressure inside the flask was assumed to be equal with the atmospheric pressure. In the experiment, the atmospheric pressure was obtained using a barometer. However, this measurement should be corrected for the temperature at which the measurement was recorded. This adjustment is important because the components of the barometer (usually mercury, brass, and glass) can expand or contract with different temperatures. The pressure was corrected using the equation below: Pc PB (1-1.8x10-4 TR) (1-3)

However, even though the pressure was corrected, the fact that it was only assumed that the vapour pressure inside the flask is equal to the atmospheric pressure might have also contributed to the error. Another assumption done in the experiment was that the molecular weight of the volatile liquid is the same with the vapour. Theoretically, this should not add any error to the calculation of the molecular weight. This is because during phase change, the composition of the substance does not change and therefore the molecular weight of the substance should not.

IV.

Sample Calculations

For trial 1 of methanol: Corrected Pressure Pc PB (1-1.8x10-4 TR) Pc 754.38mmHg (1-1.8x10-4 [28C]) Pc 750.5779248mmHg Mole fraction of water XH2O = %RH P*H2O 100PC XH2O = (75) (28.3mmHg) 100 (750.5779248mmHg) XH2O = 0.02827821 Mole fraction of oxygen and nitrogen XN2 or O2 = (1 XH2O) (percentage in dry air/100) XN2 = (1 - 0.02827821)(0.79) XN2 = 0.767660214 XO2 = (1 - 0.02827821)(0.21) XO2 = 0.204061576 Molar Mass of Moist Air MMmosit air = (XMM)nitrogen + (XMM)oxygen + (XMM)water MMmosit air = (0.767660214*28.02g/mol)nitrogen + (0.204061576)oxygen + (XMM)water = 28.54926986g/mol Volume of Moist Air/Flask/Water Vmoist air Vwater mwater water Vmoist air Vwater (mflask+water mflask at RT) water Vmoist air (166.6040g - 67.0043) 0.9962g/mL*1000 Vmoist air 0.099979623 L Mass of Moist Air mmoist air (MMmosit airPcVmoist air) / (RTr) = (28.54926986g/mol *750.5779248mmHg *0.099979623 L) / (0.0821Latm/mol-K*(28+273.15K)) = 0.114015178g Mass of Vapor

mvapor = (mflask+vapor) (mflask + mmoist air) = (67.0780g) (67.0043g + 0.114015178g) = 0.196515178g Molar Mass of Vapor MMvapor (mvaporRTR) / (PCVvapor) =(0.196515178g*0.0821L-atm/mol-K*353.15K)/ (750.5779248mmHg)( 0.099979623 L) = 55.38360309g/mol Percent Error %error = (|theoretical value actual value| / theoretical value) * 100 = (|32.04 55.38|/32.04) * 100 = 72.85% V. Summary and Conclusion

The experiment made use of the temperature-monitored vapour method to determine the molecular weight of a sample of methanol and acetone by vaporizing the substance to fill a known container at a given temperature and pressure. Using the assumptions and conditions of the ideal gas equation, the molecular weight of the samples were calculated and obtained. Since the calculations involve the ideal gas equation, certain corrections and adjustments were made to account for the deviations. In the experiment, the necessary data needed for calculation were obtained first. Using the TMVD set-up, the thermocouple temperature-time response curve was constructed. The inflexion temperatures of the samples were obtained from their corresponding graphs. Results showed that acetone have relatively low percent errors (0.91% and 0.54%), while methanol have relatively higher percent errors (72.85% and 188.45%). These might be caused by high volatility of methanol. Other errors were accounted by measurement errors, instrumental errors, and methodical errors. It was also noted that the manual determination of the inflexion temperature of the samples was quite inaccurate and difficult. The method involved certain assumptions. The method assumes that the barometric pressure is equal to the pressure of the vapour inside the flask. It also assumed that the molecular weight of the volatile liquid is significantly the same as it is in its vapour state. VI. Literature cited

ATKINS, P., and J.DE PAULA. 2006. Atkins Physical Chemistry.8th ed. Great Britain: Oxford University Press. CASTELLAN, G.W. 1983.Physical Chemistry. 3rd ed. USA: Addison-Wesley Publishing Company, Inc. SHOEMAKER, D.P., C.W. GARLAND and J.W. NIBLER. 2009. Experiments in Physical Chemistry. 8thed. New York: McGraw-Hill, Inc. (lab manual!!!!) Internet Source:

http://chem.wisc.edu/deptfiles/genchem/lab/labdocs/modules/barometer/bartemp.htm