Journal of National Taipei Teachers College, Vol. ⅩⅣ(Sep. 2001) 529~542 NATIONAL TAIPEI TEACHERS COLLEGE 529 A Connection of Ideal Gas Laws by Experiment Tzyh-lee Chang, Pi-ling Chang and Herbert C. Cheung ∗ ABSTRACT Generally, we need to perform different experiments in order to examine Boyle’s law and the law of Charles and Gay-Lussac. In this work we proposed a method which could allow us to not only investigate the preceding two laws, but also extend a connection to all the other laws such as Avogadro’s law, Dalton’s law, combined law, and the general form of ideal gas law. An analysis of the data obtained in this experiment yields acceptable results. For example, the conversion constant between the Celsius and Kelvin scales was found to be 1.15% less than the true value (=273.15), and the universal gas constant was found to differ from the true value of 0.08206(Latm/K-mol) by 1.16%. If the idea of this experiment can be applied to design a more feasible experiment for students to follow, students can not only learn all the ideal gas laws, but also know how to apply them in practical situations. Key words: Boyle’s law, the law of Charles and Gay-Lussac, Avogadro’s law, Dalton’s law, combined law, the general form of ideal gas law. ∗ Tzyh-lee Chang: Associate Professor, Department of Natural Science Education, NTTC Pi-ling Chang: Assistant Professor, Department of Nutrition Sciences, the University of Alabama at Birmingham Herbert C. Cheung: Professor, Department of Biochemistry and Molecular Genetics, the University of Alabama at Birmingham 530 Journal of National Taipei Teachers College, Vol. ⅩⅣ Journal of National Taipei Teachers College, Vol. ⅩⅣ(Sep. 2001) 529~542 NATIONAL TAIPEI TEACHERS COLLEGE 531 A Connection of Ideal Gas Laws by Experiment Tzyh-lee Chang, Pi-ling Chang and Herbert C. Cheung ∗ I. INTRODUCTION If one asks where the level of the water is inside a cylindrical bottle immersed upside down in a tank of water, many students will simply reply that the level of the water inside the bottle is the same as the water level of the tank. In fact, the water level inside the bottle is below that of the water level of the tank. This simple demonstration can motivate students to seek why there are differences in the water level. As a matter of fact, it can be explained by the equilibrium of pressure which is reached between the inside pressure of dry air plus vapor pressure of water in the upside down cylindrical bottle and the external pressure of atmospheric pressure plus water pressure in the tank. Furthermore, with a few measurements on the different depths of the water levels both inside and outside the cylindrical bottle, one can quantitatively link the experimental data to all the ideal gas laws. The experimental method presented is simple in theory, safe and straightforward in practice. II. THEORY OF IDEAL GAS LAWS A sample of gas can be characterized by four variables: the volume V, the temperature T, the pressure P, and the number of moles n. For an ideal gas, simple ∗ Tzyh-Lee Chang: Associate Professor, Department of Natural Science Education, NTTC Pi-ling Chang: Assistant Professor, Department of Nutrition Sciences, the University of Alabama at Birmingham Herbert C. Cheung: Professor, Department of Biochemistry and Molecular Genetics, the University of Alabama at Birmingham 532 Journal of National Taipei Teachers College, Vol. ⅩⅣ relationships, known as the ideal gas laws, have been established concerning these variables: Boyle’s law P1V1=P2V2 T and n constant (1) Avogadro’s law V1/n1=V2/n2 P and T constant (2) Dalton’s law P1/n1=P2/n2 V and T constant (3) The law of Charles V1/T1=V2/T2 P and n constant (4) P1/T1=P2/T2 V and n constant (5) and Gay-Lussac Combined law P1V1/T1=P2V2/T2 n constant These individual relationships imply a more general relationship: PV=nRT, (6) (7) where R is known as the universal gas constant. In this experiment we can study all these laws from the experimental data. In addition, we can also examine the quality of data by comparing the derived conversion constant between the Celsius and the Kelvin scale and the universal gas constant with well-known values of 273.15 and 0.08206Latm/K-mol, respectively. III.EXPERIMENTAL SECTION Mercury has commonly been used to study the Boyle’s law in general science labs (Hermens, 1983; Hein, et al., 1992). However, these experiments must be performed cautiously because spilled mercury can be very hazardous. To keep away from danger, the use of hypodermic syringes was proposed instead (Davenport, 1962). Boyle’s law was examined by taking the volume readings of a gas trapped in the syringe by piling books onto the piston. In addition, Charles’ law could also be examined by taking the volume readings of a gas in a syringe which was immersed in a liquid bath maintained at various temperatures (Davenport, 1962). In our experiment we used water rather than mercury. Thus our experiment has the same advantage of safety as the use of hypodermic syringes. Furthermore, to the best of our knowledge our experiment has been the first one reported so far that can lead all the ideal gas laws to be learned by one experiment. In fact, the idea of our experiment was obtained from a previous study about the relationship between candle flame and oxygen (Chang, 1999). The equipment and materials used in our experiment include two thermometers (a mercury thermometer and a digital thermometer, Sensortek model BAT-12), one A Connection of Ideal Gas Laws by Experiment 533 barometer (Fisherbrand compact digital barometer), one measuring tape (or a ruler), distilled water, two stands and two utility clamps, four graduated glass cylinders (2 2L, 1 1L, and 1 500mL), and a few volumetric flasks and pipettes. The experiments were performed at two different temperatures. The first measurement was done in the lab at 20.9°C and the second in the cold room at 4.8°C. These two temperatures happened to be the lab temperature and the cold room temperature during the time of data collection. It is purely for the purpose of simplicity to take the measurements at 20.9°C in the lab and 4.8°C in the cold room, respectively. Consistent results should be obtained if data were taken at different lab and cold room temperatures. Firstly, we filled the two 2L cylinders with distilled water till close to the brim, then inserting a 1L cylinder and 500mL cylinder with their open ends down into the 2L cylinders, respectively. It is important to hold the cylinder vertically when inserting it into the water. Otherwise bubbles might incur suggesting air leakage and thus contribute to the inaccuracy of data analysis. The data were taken by measuring the distances between the open end of the upside down cylinder and the water levels both outside and inside this cylinder. Four sets of data were obtained for each set-up by inserting the cylinders into different depths under the water. We actually obtained different depths by changing the amount of water using a pipette-aid filler/dispensers rather than by moving the upside down cylinder to the desired positions. In order to avoid the possible problem of equilibrium between water vaporization and condensation, we waited for about one hour between each data taken. After taking the data in the lab, we moved the whole set-up without removing the 1L and 500mL cylinders from the 2L cylinders in which they were inserted to the cold room and left them there for overnight. The procedures used in the cold room were exactly the same as those used in the lab. To monitor the temperature, the probe of the digital thermometer was inserted in the middle of the upside down cylinder by using Scotch tape to fix its cable to the wall of cylinder. The temperatures recorded directly from inside of the cylinder are quite consistent with those recorded by using a mercury thermometer inserted in the water surrounding the upside down cylinders. The temperatures varied within ±0.2°C during the time of data collection in the lab and in the cold room. 534 Journal of National Taipei Teachers College, Vol. ⅩⅣ IV. RESULTS The data obtained from 1L cylinder and 500mL cylinder at lab temperature (20.9°C) are shown in Tables 1 and 2, respectively. Similar data using the same two cylinders at 4.8°C are also shown in Tables 3 and 4. The first two columns in these four tables are experimental data, on which the calculated and measured data listed in the last three columns are based. The values in the first columns are the distances (d) between the open end of the upside down cylinder (1L or 500mL) and the water surface outside the cylinder. The distances (w) between the open end and water surface inside were also measured corresponding to each of the four different depths shown in the first columns, and they are listed in the second columns in all four tables. No bubbles were observed when inserting the cylinders into water thus indicating that there is no gas leak. During the experiments, the atmospheric pressures remained as 995mb in the lab and 991mb in the cold room (both readings from the digital barometer), respectively. We calibrated the digital barometer with a Fisher mercury barometer. A correction value of 5.331×10-3atm should be added to the above readings. Table 1 Data for 1L cylinder at 20.9°C and 995mb. d / cm w / cm (d-w)÷1035.99 / atm V/L PV / atm-L 40.00 1.54 0.0371 1.1981 1.1982 35.00 1.35 0.0325 1.2035 1.1980 30.00 1.20 0.0278 1.2077 1.1965 25.00 1.04 0.0231 1.2125 1.1956 Table 2 Data for 500mL cylinder at 20.9°C and 995mb. d / cm w / cm (d-w)÷1035.99 / atm V/L PV / atm-L 32.00 1.14 0.0298 0.61548 0.6110 28.00 1.02 0.0260 0.61770 0.6109 24.00 0.89 0.0223 0.62010 0.6109 20.00 0.77 0.0186 0.62230 0.6108 A Connection of Ideal Gas Laws by Experiment 535 Table 3 Data for 1L cylinder at 4.8°C and 991mb. d / cm w / cm (d-w)÷1033.96 / atm V/L PV / atm-L 40.00 4.36 0.0345 1.1185 1.1290 30.00 3.95 0.0252 1.1305 1.1306 20.00 3.55 0.0159 1.1420 1.1315 10.00 3.14 0.00663 1.1536 1.1323 Table 4 Data for 500 mL cylinder at 4.8°C and 991mb. d / cm w / cm (d-w)÷1033.96 / atm V/L PV / atm-L 32.00 3.48 0.0276 0.57502 0.5764 24.00 3.18 0.0201 0.57983 0.5769 16.00 2.88 0.0127 0.58493 0.5777 8.00 2.65 0.00517 0.58893 0.5772 The pressure exerted by the air trapped inside the upside down cylinder differs from atmospheric pressure by an amount equal to the water pressure due to the difference of water levels (=d-w). This height should be added to atmospheric pressure (both in atm) to give the total pressure on the gas sample. The height in atm is shown on the third column in each of the four tables. The value of 1035.99 shown in the headings of the third columns in Tables 1 and 2 and the value of 1033.96 in Tables 3 and 4 allow for conversion of the heights in cm of water to atmospheres. They are obtained from the following eq: 101,325Nt/m2 = ρ(kg/m3)×g(m/s2)× H(m), where g = 9.80m/s2, and ρ is the density of water. 3 ° 3 The values of ρ are ° 0.9980137g/cm at 20.9 C and 0.9999654g/cm at 4.8 C, respectively (Weast, 1986). The fourth columns on each of the four tables represent the volumes of trapped air inside the cylinders corresponding to different settings. To more accurately measure the volume of the trapped air we fill the cylinder with water using volumetric flasks and pipettes to the heights corresponding to the readings listed in the second columns of all four tables (i.e., the distances from the open end). The total pressure is the sum of atmospheric pressure and the pressure due to the difference of water levels (data in the third columns of all tables). The partial pressure P due to dry air is corrected by subtracting the vapor pressure of water from 536 Journal of National Taipei Teachers College, Vol. ⅩⅣ the total pressure. The vapor pressures of water are 18.536mmHg at 20.9°C and 6.453mmHg at 4.8°C, respectively (Weast, 1986). The products of P and V are listed in the last columns. Here we are only concerned about the number of moles of dry air because it is assumed to be the same for all the four different settings, whereas the number of moles of water vapor is different and thus the total number of moles of gases is different. Note that the number of moles of dry air related to the data in Tables 1 and 3 is the same, and so is that related to the data in Tables 2 and 4. V. DISCUSSION 1. Boyle’s Law The average values of the products PV are shown as follows: 1L cylinder at 20.9°C ° 500mL cylinder at 20.9 C ° 1L cylinder at 4.8 C ° 500mL cylinder at 4.8 C <P1V1> = 1.1971±0.0012 (8) <P2V2> = 0.6109±0.0001 (9) <P3V3> = 1.1308±0.0014 (10) <P4V4> = 0.5771±0.0005 (11) The constancy of these PV products (Tables 1 to 4) proves the validity of eq (1) and thus the validity of Boyle’s law. However, since the pressure and volume changes are not large, good results can be obtained under conditions of stable temperature and atmospheric pressure only. The subscripts specify the cylinder and the experimental conditions under study. It is convenient to use them in the following discussion. 2. Avogadro’s Law From the values of PV shown from eqs (8) to (11), we can see that PV = C′(T,n), where C′(T,n), is a constant that depends on temperature and the number of moles of dry air. Since the data in Tables 1 and 2 were obtained under the same temperature, then from Boyle’s law, we know that under 1atm and 20.9°C, the volume of trapped dry air is equal to the value of the product PV. Thus the ratio of the value in eq (8) to that in eq (9) should reflect some relationship between the moles of dry air in 1L cylinder and 500mL cylinder. The ratio is 1.9595. The same line of reasoning can be used to find a ratio of 1.9596 for the same two cylinders under 1atm and 4.8°C. These A Connection of Ideal Gas Laws by Experiment 537 two ratios are very close to the ratio of the volume of 1L to 500mL cylinders (1247cm3/637cm3 = 1.96). From these close ratios, we can deduce that the volume of dry air is proportional to its number of moles under conditions of constant temperature and pressure. Actually, this is consistent with Avogadro’s law which states that under conditions of constant temperature and pressure, equal volumes of gases contain equal number of particles. Therefore, the dependence of C′(T,n) on the number of moles of dry air can be written as C′(T,n) = nC(T), where C(T) is a constant that depends only on temperature. So far the equation of state can be further described as PV = nC(T), which satisfies both the laws of Boyle and Avogadro. The relationship of P1V1/n1 = P2V2/n2 under constant temperature will be used next. 3. Dalton’s Law of Partial Pressure We notice that Dalton’s law of partial pressure has already been assumed, since we calculate the pressure of dry air by deducting the vapor pressure of water from the total pressure. Dalton’s law of partial pressure states that under conditions of constant volume and temperature, the number of moles of different molecules are responsible for the partial pressure exerted by them. We can actually examine this by the same method as above (however, now we assume the volume of trapped dry air to be 1L rather than the pressure at 1atm as we did previously). Under conditions of the same volume for trapped dry air (=1L), we have <P1V1>/<P2V2> = n1/n2 = P1(assuming V1=1L)/P2(assuming V2=1L) = 1.1971/0.6109 = 1.9595 (12) Similarly, <P3V3>/<P4V4> = n3/n4 = P3(assuming V3=1L)/P4(assuming V4=1L) = 1.1308/0.5771 = 1.9596 (13) Note that n1 = n3 and n2 = n4. If the gas molecules are assumed to behave ideally, then the consistent results shown in eqs (12) and (13) may be evidence of the validity of Dalton’s law. 538 Journal of National Taipei Teachers College, Vol. ⅩⅣ 4. The Law of Charles and Gay-Lussac This law states that at constant pressure the volume of a given mass of gas is directly proportional to its temperature on the Kelvin scale. By assuming that the pressure is at 1atm, <P1V1>/<P3V3> = V1/V3 = 1.1971/1.1308 = 1.0586 = (t1+α)/(t3+α), (14) where α is the conversion constant between the Celsius and Kelvin scales, and t1 and t3 are the temperatures in degrees Celsius. The values of t1 (=t2) and t3(=t4) are 20.9°C and 4.8°C, respectively. The value of α found is 270. Similarly, <P2V2>/<P4V4> = V2/V4 = 0.6109/0.5771 = 1.0587 = (t2+α)/(t4+α). (15) Here the calculated value of α is also 270. These values differ from the known value of 273.15 by 1.15%. The significance of α is that at -α(°C) the volume of dry air is zero (i.e., no dry air is in the gas phase). The law of Charles and Gay-Lussac also states that at constant volume the pressure of a given mass of gas is directly proportional to its temperature on the Kelvin scale. Assuming that the volume is fixed at 1L, we can obtain similar results as above by a similar line of reasoning. <P1V1>/<P3V3> = P1/P3 = 1.1971/1.1308 = 1.0586 = (t1+α)/(t3+α), (16) <P2V2>/<P4V4> = P2/P4 = 0.6109/0.5771 = 1.0587 = (t2+α)/(t4+α). (17) Obviously, the value of α obtained is the same as above and it means that at -α(°C) the pressure of dry air goes to zero, as it should be because there is no dry air in the gas phase. 5. Combined Law From the law of Charles and Gay-Lussac, we can see that for a given mass of dry air PV/T = constant. Thus we can use this equation to find volumes under STP (1atm, 0°C) conditions. The V1(STP) is found to be 1.112L by solving the following equation: <P1V1>/(273.15+20.9) = (1atm)V1(STP)/273.15. Since under STP conditions one mole of ideal gas occupies 22.41L, n1 = V1(STP)/22.41 = 4.961×10-2moles. By solving similar equations, we find V2(STP) = 0.5675L, V3(STP) = 1.111L, V4(STP) = 0.5671L, and the corresponding numbers of moles are n2 = 2.532×10-2moles, n3 = 4.958×10-2moles, and n4 = 2.530×10-2 moles, respectively. The values of V1(STP) A Connection of Ideal Gas Laws by Experiment 539 and V3(STP) or (n1 and n3) are close to each other, as they should be, and so are the values of V2(STP) and V4(STP) or (n2 and n4). 6. A More General Form of Ideal Gas Law For all the laws discussed above, we observe that they are all special cases of a more general form of ideal gas law, which can be written as PV = nRT, where R is the universal gas constant. The value of R can be found from the number of moles by solving R = (<P1V1>– <P3V3>)/ [(n1/2+ n3/2)(t1–t3)] = (1.1971–1.1308) /[(4.9594×10-2)(20.9– 4.8)] = 0.08295 (L-atm/K-mol) for the case of 1L cylinder. A similar computation yields R = 0.08307 (L-atm/K-mol) for the case of 500mL cylinder. The average value differs from the true value of 0.08206 (L-atm/K-mol) by 1.16%. VI. CONCLUSION Ideal gas laws are discussed in every basic physics and chemistry textbook. It is fundamental to know them before a further understanding of gaseous behavior is obtained. The experiment described here provides a straightforward way to reveal the validity of Boyle’s law and the law of Charles and Gay-Lussac. Subsequently, by applying these two laws, we are able to connect all the other ideal gas laws including Avogadro’s law, Dalton’s law, combined law, and the general form of ideal gas law. Although the experiment presented here can connect all the laws, we notice that the change in the volumes of trapped air corresponding to different settings is not very significant. Moreover, this experiment may not be feasible for most of the students because there might not be a cold room available for them. It is our next goal to design a more feasible experiment for improvements. ACKNOWLEDGMENT Tzyh-Lee Chang gratefully acknowledges the support from National Taipei Teachers College during his sabbatical leave. He also appreciates Professor Cheung’s cordial invitation to his laboratory at the University of Alabama in Birmingham. 540 Journal of National Taipei Teachers College, Vol. ⅩⅣ REFERENCES Chang, T. L. (1999). An extension of the relationship between candle flame and oxygen - a quantitative study related to the contents of the learning activity 2 of unit 3 in elementaryschool natural science textbooks volume 9. J. NTTC, 12, 301-316. (in Chinese) Davenport, D. A. (1962). Hypodermic syringes in quantitative elementary chemistry experiments: I, the gas laws. J. Chem. Educ. 39(5), 252-255. Hein., M., Best, L. R., Miner, R. L., & Ritchey, J. M. (1992). College chemistry in the laboratory. 5th Ed., Pacific Grove: Brooks/Cole Publishing Co., p. 123-140. Hermens, R. A. (1983). Boyle’s law experiment. J. Chem. Educ. 60, 764. Weast, R. C., Ed. (1986). CRC handbook of chemistry and physics (67th Ed.). Boca Raton: CRC Press, Inc., pp. D-190, F-4. 國立台北師範學院學報,第十四期(九十年九月)529~542 國立台北師範學院 541 一個連結所有理想氣體定律的實驗 張自立、Pi-Ling Chang 、Herbert C. Cheung ∗ 摘 要 一般需要進行不同的實驗來驗證波義耳定律和查理–蓋、呂薩克定律。本文 中我們提出一個可驗證這兩定律又可延伸關連到所有其它定律如亞佛加厥定 律、道耳頓定律、組合定律和廣義理想氣體定律的新實驗。從實驗所得數據 中,我們得到不錯的結果,例如:分析得到的攝氏和凱氏溫標轉換值只與已知 值 (=273.15) 相 差 1.15% ; 另 外 , 所 得 到 的 普 遍 氣 體 常 數 值 , 也 只 與 已 知 值 0.08206(L-atm/K-mol)相差 1.16%。若本實驗的構想可被應用以設計一個對學生更 可行的實驗,則學生不僅能學到所有理想氣體定律,且能知曉如何實際應用這 些定律。 關鍵詞:波義耳定律、查理–蓋、呂薩克定律、亞佛加厥定律、道耳頓定律、組 合定律、廣義理想氣體定律。 ∗ 張自立:自然科學教育學系副教授 Pi-ling Chang:美國阿拉巴馬大學(伯明罕)營養科學系助理教授 Herbert C. Cheung:美國阿拉巴馬大學(伯明罕)生化和分子遺傳學系教授 542 國立台北師範學院學報,第十四期