MEASUREMENT OF TEMPERATURE, IV. EXPERIMENTS INVOLVING GASES —<—— —<——= PRESSURE, VOLUME, AND MASS TEMPERATURE ‘The measurement of gas temperatures may be done by ‘any method used for measuring temperature. In Introductory Chemistry laboratory. the usual method will be to use a mercury-in-glass thermometer. It will be ‘assumed that such thermometers are sufficiently accurate for most of the required temperature measurements. If there is any doubt about the accuracy of a thermometer. it should be calibrated against at least a couple fixed Temperature points bracketing the range in which it will be used. Before use, thermometers should be carefully examined to make certain that there are no gaps in the ‘mercury thread in the thermometer capillary and that there are no cracks in the thermometer glass, particularly the sensing bulb. If such defects are found, the thermometer should not be used, and should be referred to the laboratory instructor for repair or disposal ———_— Jn use, care should be taken not to drop the] thermometer or hit it against hard surfaces. Mercury is a] oxic heavy metal; breaking a thermometer will release the| mercury in almost all cases. If a thermometer should be} broken, notify the laboratory instructor. ‘The thermometers used in the laboratory will be calibrated in Celsius temperatures. Two fixed temperatures oon the Celsius temperature scale are the water-ice point’ which is at zero degrees Celsius (0°C or 0 C, the deere symbol generally not being written) and the steam point which is at 100 C ? at a standard atmosphere pressure (760 mm He). ‘The most common laboratory thermometer has 2 temperature mark each degree: tenths of degrees may be estimated between the marks. Such thermometers are ‘commonly available to cover the range from about -10 C to 110 C. For mote precise readings, thermometers are available which are marked at every tenth degree: — 1 The thermometer is used to measure the temperature of a slurry of crushed ice and water. ‘The steam point is harder to measure than the ice-water point. The thermometer is suspended in the steam above boiling water so that water condenses on its bulb. A correction to the temperature is made if the ambient pressure is not 760 mm Hg. hundredths of degrees may be estimated. The range 1s generally from about -10 C to about 51 C, Care should be taken never t0 heat a thermometer above its maximum readable temperature; the thermometer may break or become inaccurate. Breakage will release mercury ‘The relationship between Celsius and Fahrenheit temperatures? is given in most general or introductory chemistry texts; refer to your text For gases. the temperature which is most useful is the absolute or Kelvin temperature. The degree size on the Kelvin scale is identical with the degree size on the Celsius scale but zero degrees Kelvin (0 K or absolute 2e70) is @ temperature which corresponds to -273.15 C. To convert Celsius temperature 10 Kelvin temperature, and vice versa the relationship is TK = tC + 273.18 where T is the Kelvin temperature, and t is the corresponding Celsius temperature. Thus 0C = 273.15K In any calculations involving gases, the Kelvin temperature should be used, although the temperature will be measured experimentally as a Celsius temperature PRESSURE In gas measurements, itis important to realize that pressure is a variable which must be either held constant throughout the experiment—and/or must cancel out of the caleulations—or must be measured as part of the dara fathered. Pressure is force per unit area: force is mass times acceleration. In symbols P= FIA and Fema In St units, F = (kg){rvs?) (kgyeis*Vien?) Pp “The unit Newton/m? is a pascal, abbreviated Pa In cs units F = (gifervs'] = P= dynesiom? —, > Om the Fatvenheit (F) scale, the ice point is 32 F and the steam point is 212 F.EXPERIMENTS INVOLVING GASES In order to measure pressure. then. it is necessary 10 measure both force and the area over which the force is exerted, In most applications in chemistry the measurements are. done simultaneously by means of barometer or manometer. A torricellian barometer consists of a long tube closed at one’ end and filled witha liquid. The tube is then invered in an open pool of the liquid, The figure at the right illustrates a simple torricellian ‘barometer; the height, h of liquid in the tube would be measured with a scale, such as a meter stick, with its zero at the pool surface. The length of liquid column supported in the tube is taken as a measure of the pressure on the liquid surface in the dish, What is actually measured as pressure isthe pressure exerted by the liquid column at the Tiquid surface on an area equal to the cross-section of the column, This pressure is balanced against the pressure being exerted on the pool by the outside (ambient) atmosphere, Because of this balance, the column height corresponds to the ambient pressure ‘The column height. then. depends on the ambient pressure and on the density of the liquid, which affects the mass of the liquid in the column. The height does nor depend on the diameter, or cross-sectional area, of the tube because the force at the surface is determined only by the height; any unit area at the surface will have the same force acting on it. For a mercury-filled* barometer—the ‘most common type—the height of the mercury coluran at sea level on a fair day will be around 760 millimeters ‘This value i taken as the standard armosphere, abbreviated 1 standard atm = 760.0 mm Hg 60.0 torr ‘The torr unit is the accepted name for “mm Hg” and recognizes the work of Torricelli in developing the barometer. In some other common units, the standard atmosphere is 14.70 pounds/in’ (psi), or 1.013 X 10" pascals (Pa), ‘Another common type of barometer is the aneroid barometer. Aneroid barometers operate by enclosing a volume of gas (usually air) in a closed bellows. As the — © The density of mercury at 0 C is 13.5955 gmL. Ww—2 pressure outside the bellows increases or decreases. the bellows will contract or expand. The movement of the bellows causes a needle to move across a scale calibrated in pressure units. Aneroid barometers must be calibrated against a torricellian barometer and are subject to errors due to temperature and altitude—both of which also cause the bellows to contract or expand. Torricellian barometers are also subject to errors due to temperature and the vapor pressure of the filling liquid As the temperature of the filling liquid increases, its density decreases. As a result a longer column of liquid will be supported by the same pressure. To avoid confusion as 10 what a given reading of the barometer means, all readings are reduced to a temperature of 0 C. Appendix A contains a table which lists temperature corrections to be applied to mercury-filed barometers with brass scales—the type of barometer used in the chemistry laboratories. These corrections are to be subtracted from the reading obtained from the barometer. In the barometer tube, the space above the liquid is generally considered to be a vacuum. In fact. this space ‘contains vapor of the filling liquid. The vapor pressure of mercury at 25 C is about 0.004 mm Hg which is negligible in an instrument usually read to only +0. mm. If a volatile liquid, such as water (vapor pressure at 25 C 23.8 tor) is introduced above the mercury in a barometer, the top of the mercury column will fal by an amount equal to the vapor pressure of the liquid, in this case, by 23.8 mm, This method could be used to measure vapor pressures of volatile liquids: it is not used because there are simpler, and safer’, ways to get vapor pressures. A ‘water-filled barometer would have to be about 40 feet long ‘and would have a built-in error of about an inch (25.4 mm) because of the vapor pressure of the water. ‘The common mercury-filled barometer has a length of about one yard. This is too large an instrument 10 incorporate into the design of most apparatuses for laboratory use. In addition, the barometer can only be read to 0.1 torr (mm Hg) with any accuracy; small pressures for pressure differences would be difficult to read. To measure pressure differences a manometer is used. Manometers come in many designs: the most common, illustrated on the next page. is a U-shaped-tube. or U-tube, partially filled with a liquid. If both ends of the U-tube are ‘open {0 the atmosphere (or are connected to the same 5 Mercury, like most heavy (high atomic weight) metals, is toxic. The vapor can be absorbed through the lungs and skin, The metal tends to accumulate in biological systems and can reach toxic levels within the system, even though the system was never exposed 10 a toxic level of the metalcontainer) there will be no difference in the liquid level of the two arms of the tube. On the other hand, if one arm is connected to a container of gas at higher than atmospheric pressure and the second arm is ‘open. to the atmosphere, the liquid level in the open arm will be higher than in the gas arm The difference in level, d, measures the difference between the gas pressure and the atmospheric. pressure; the gas Pressure is equal to the ambient aimospheric pressure (as measured by a nearby barometer) ‘Plus the difference d (converted to appropriate units). If the liguid is water with a density about 1/13.6 times that of mercury, a 0.1 torr difference is now 1.36 mm H,O, an easily seen and measured difference. Most manometers make use of liquids which have low densities (close to that of water) and low vapor pressures in order to amplify the difference in pressures. Not all manometers look like Ustubes. Any liquid- filled tube which communicates at its ends with different gas reservoirs (one of which may be the atmosphere) will act as « manometer. Ifthe levels of liquid are the same, the pressures atthe two ends must be the same also. We can make use of this manometric principle to set the pressure inside a container to atmospheric pressure. To summarize, pressures may be measure absolute terms such as newtons per square meter, pounds per square inch, or any other force unit| per area unit. In practice, it is generally more| convenient to measure pressure in a relative unit| [such as millimeters of mercury, atmospheres, or inches of mercury. Barometers measure these| relative pressures, although a barometer could be| calibrated in absolute terms. Manometers measure| differences in pressure between two sources and| may be used in the laboratory to set the gas| pressure inside a container to that of the| lsurrounding atmosphere without opening the| lcontainer to the atmosphere. VOLUME Because gases fill any container into which they are placed, the measurement of gas volumes poses an unique challenge in the laboratory. In general there are two ‘methods for such measurements: a direct measurement or EXPERIMENTS INVOLVING GASES fan indirect measurement. Direct measurement of gas volumes can be done by means of gas burets or pipets or by filling a previously calibrated container such as a flask of bottle with the gas. Indirect methods usually involve the displacement of some liquid by the gas, followed by ‘measurement of the liquid volume. Direct Measurement Methods Gas burets or pipets operate in the same manner as burets and pipets for measuring liquid volumes with the major difference being that a suitable liquid must be used to contain the gas within the buret or pipet. The liquid used for the measurement must be inert toward the gas to be ‘measured and must not dissolve the gas to any extent. It is also convenient if the liquid has a very low volatility so that appreciable amounts of the liquid’s vapor are not Present in the gas trapped by the liquid. If one imagines an ‘ordinary buret or pipet (see pages Ill — 5 and 6) with the air serving as the trapping fluid for a liquid and then reverses the roles so that liquid traps gas, one has the principle upon which the gas buret/pipet operates. The liquid is used as a movable piston to draw gas into the buret/pipet or to force gas from the buret/pipet. Pipets generally have a fixed volume which they will contain or deliver. Burets, like their counterparts for liquids, generally have graduations which allow variable known Volumes to be measured. ‘The simplest gas buret is a calibrated tube closed at cone end. In use the tube is filled with a liquid to the brim, then inverted in a reservoir of the liquid. Gas is introduced into the inverted tube by means of a piece of tubing and is trapped above the liquid. The volume of the gas is read from the tube. Major problems with such a buret are the inability to know the pressure of the gas inside the tube and the limitation on the length of the tube. The tube may be treated as a manometer; thus, the pressure may be approximated by measuring the height of liquid and using its density—assuming it is not mercury—to correct the pressure, The outside (atmospheric) pressure must be ‘known. Immersion of the tube in a cylinder containing the liquid so that the liquid levels inside and outside the tube are equal sets the gas pressure at the ambient laboratory pressure; note that the liquid levels are serving as a manometer. Length of the tube will only be a practical problem if the containing liquid is mercury; any length greater than the ambient atmospheric pressure would result im an apparent gas pocket at the upper end of the buret since the pressure would be unable to support the liquid column totaly. If a volatile liquid is used, corrections for the vapor pressure (or vapor volume) must be made In Experiment B, page 1V— 13 , the volume of a Ww—3EXPERIMENTS INVOLVING GASES 250 mL flask will be determined to four significant figures. ‘The flask will be filled with dry, pure carbon dioxide gas and the mass of the carbon dioxide determined. The flask is filled by simply allowing CO, gas to run through it while it sits on the laboratory bench top. The pressure and ‘temperature will be the ambient pressure and temperature, easily obtained by reading the barometer and a thermometer. The volume will be known; the flask stays filled because of the high density of CO, gas compared to that of the air outside the flask. The calculations and ‘method have been used previously (see page Il — 5) as an example of the use of significant figures. Indirect Measurement Methods Indirect measurement of gas volumes may be done by uusing the gas to displace a liquid into a container. The displaced liquid’s volume is then measured by a suitable volumetric method; the liquid volume is assumed to be the same as the gas volume. It is also possible to displace the liquid from a graduated container and to measure the gas volume directly. In using liquid displacement to measure a gas volume, it is convenient to set the gas pressure at the laboratory (barometric) pressure before measuring the liquid volume ‘and while the displaced liquid is still in communication with the liquid which was not displaced. This can be done ‘by making sure that the liquid level inside the gas container and the liquid level in the container which receives the displaced liquid are the same. Under this condition, the Pressure inside the gas container, from which the liquid was partially displaced, is the same as the laboratory Pressure. The laboratory pressure may be measured with ‘a barometer. This method will be used in Experiment A, page IV — 6, to determine the volume of oxygen gas generated. The apparatus that allows equalization of the pressures js illustrated in that experiment. MASS ——— ‘The measurement of the mass of a gas sample is done in a straightforward way by simply weighing the gas sample trapped in some kind of container, Since some ‘gases are lighter than air and some heavier, a container of Bas may appear as lighter or heavier than the same container filled with air. ‘The direct approach to establishing the mass of the gas ‘would be to evacuate the container with a vacuum pump and then weigh the empty container, Gas bulbs for this Purpose are usually spherical, the strongest shape for resisting the implosion which could result, and heavy- WV—4 Walled. A stopcock allows gas to be evacuated ot admitted to the bulb. Typically, the bulb is about 250 mL in volume. Major concems with the use of evacuated gas bulbs are the possibility of a dangerous implosion and the greater possibility of leaks around the stopcock. An indirect approach is to fill a container whose volume is known, or can be determined, with a known gas at atmospheric pressure. The mass of such a bulb will be due to the mass of the bulb plus the mass of the known 2. If the density of the gas is known from the literature, or can be calculated, the mass of gas is available from the Volume times the density. Subtracting the mass of the gas from the total mass yields the mass of the empty bulb. This method, using a stoppered 250 mL flask as the bulb will be used in Experiment B, page IV — 13, to determine the mass of CO, gas which fills the flask, ‘A second indirect approach to establishing the mass of ‘a known volume of gas is to use the gas laws to calculate the number of mols of gas, from which the mass in grams ‘may be calculated. At ordinary temperatures and pressures (around room temperature and one atmosphere), many gases obey the so-called ideal gas law well enough to give reasonable results from such calculations. A brief discussion of the ideal gas law and other gas laws follows. Most introductory chemistry texts cover the gas laws and the ideal gas law in great detail..Refer to any such text for wider coverage. The Ideal Gas Law ‘The ideal gas law combines the historically significant laws of Boyle, Charles, and Avogadro into a single statement: PA wRT where P is pressure, V is volume, n is number of mols, and T is the Kelvin temperature. R is the universal or ideal ‘gas constant, which has the same value for all gases, Provided the gases are behaving ideally. “The value of R in various units is 0.08206 L-atm/(mol'k) 8.3145 kPa-dm*/(mol-K) 8.3145 joulesi(molK) 41.987 cali(mol-K) The first two values are of more use in gas calculations; the second pair of values are most useful in energy calculations. Note that a kPa-dm’ must be a joule; a joule () is a dyne-cm or 107 ergs. ‘The ideal gas law contains four variables and a constant. If any three of the variables are known, thefourth may be calculated from the law. Since one variable, the number of moles can be calculated from mass and gram-molecular-weight, n= wiM Where w is the mass in grams and M is the gram- ‘molecular-weight in grams per mol, it is possible to calculate the mass of gas if pressure, volume, temperature, and molecular weight are known, The Combined Gas Law Since R isa constant, it is possible to solve the ideal gs law for R R= P-VinT ‘This equation must hold for an ideal gas under all conditions, therefore, if a gas is measured at two sets of pressure, volume, and temperature, PLVJT, = PpViT, where the subscripts indicate the two sts of conditions This combined law is sometimes called the general gas law. With six variables, five must be known in order 0 calculate the sixth. Dalton's Law of Partial Pressures The previous laws apply to single gases, In many ‘experiments, gases may be mixed so that two or more gases are responsible for the pressure or volume measured. This is the case, for example, if a single pure gas is trapped over a liquid which has an appreciable vapor Pressure. In a mixture of gases, each gas totally fills the container; that is, the gas in the container is a ‘homogeneous mixture (solution) of the gases making up the mixture. While some chemical calculations can be used 10 obtain a partial volume for each gas, in effect breaking the total volume of the mixture into “compartment volumes” which contain single gases, this model has no basis in realty. The gases in a mixture are not in separate volumes On the other hand, if the gas molecules in the mixture behave independently of each other, having no ot negligible attractive forces, then the gases should exert EXPERIMENTS INVOLVING GASES their pressures independently of each other. In effect, each gas behaves as if it is present by itself in the total volume. The total pressure of the mixture is then the sum of the individual gas pressures. This is Dalton’s law: as a statement Pai =P, + Py + Py tom where the P, , Py etcetera are the partial pressures of the gases in the mixture. The practical use of Dalton’s law occurs frequently when a gas is trapped over a has an appreciable vapor pressure. The gas thus contains some of the vapor of the liquid as a second component The total pressure is made up of the gas pressure plus the vapor pressure of the liquid at the temperature of the liquid; that is, Prat © Poas * Proper If the gas pressure alone is desired, the vapor pressure must be subtracted from the total pressure. The gas pressure, P,,, would be used in calculations for any ‘variable of the gas. If the volume of the gas is desired, the partial pressure of the gas, Poa, = Prosi ~ Pyaporr Would be used to calculate the volume. In many directions, this is referred to as obtaining or calculating the dry volume of the ‘888. This use is demonstrated in Experiment A, page IV —6, in which the dry. volume of oxygen gas trapped over water is desired. A table of vapor pressures for water is included in Appendix A. ‘Standard Temperature and Pressure In order to compare different gases under the same conditions, a set of standard conditions are defined. The standard conditions are often referred to as the standard temperature and pressure, abbreviated STP or SC. The standard temperature is defined as 0 Celsius (273.15 K) and the standard pressure is 1 atmosphere (760 torr, 1.013X10* pascals). Under these conditions, an ideal gas hhas a molar volume of 22.414 Limol. This volume is called the standard molar volume. Ww—5EXPERIMENTS INVOLVING GASES WV—6EXPERIMENTS INVOLVING GASES. EXPERIMENT A: DETERMINATION OF THE STANDARD MOLAR VOLUME OF OXYGEN GAS Canna a a i Ret OBJECTIVES In this experiment you will: (2) use the gas laws to correct the observed volume of a wet gas to dry STP conditions; (2) read a mercury barometer and find and apply appropriate corrections to the reading; (3) use the manometric principle to obtain the pressure of a trapped gas; (4) use significant figures in calculations involving addition, subtraction, multiplication, and division; (5) determine a value for the standard molar volume of ‘oxygen gas and calculate a percent error. BEFORE COMING TO LABORATORY Before coming to the laboratory session for this experiment, you should do the following:* 1. Read the sections in this manual on gases—how to ‘measure their properties; how gases behave—and the sections on measuring volume, pressure, mass, and temperature. 2. Use the index or table of contents in your text to find the pertinent sections covering the topics listed above and read those sections in the text. 3. Read the experiment thoroughly. Take notes in the wide margin provided. High-light the parts which call for you to take some action. Pay particular attention to any CAUTION notes in the experiment. Plan your approach to the experiment and getting the data. Look up in your text or this manual, or ask your instructor about, any material for the experiment which you do not understand. INTRODUCTION ‘The molar volume of oxygen gas at standard It is assumed at this point that you have read and understood the sections on SAFETY IN THE LABORATORY and SIGNIFICANT FIGURES. temperature and pressure (STP) will be obtained by determining ‘the volume at a known temperature and pressure of a weighed quantity of oxygen gas. The volume will be corrected to STP and the grams of gas 10 moles; the molar volume (STP) can then be calculated. ‘The oxygen will be generated by heating a mixture of Potassium chlorate, KCIO;, and manganese dioxide, MnO,, ‘The stoichiometric reaction is 2KCIO, [+ MnO] + 4 > 2KCI + 30, [+ MnO] ‘The manganese dioxide is not changed in the reaction; it serves as a catalyst and speeds up the reaction of the Potassium chlorate but is not reacted itself. This is indicated by enclosing the MnO, formula in brackets’; the amount of MnO, used is not critical so long as an intimate mixture of the MnO; and KCIO, is present. All of the reactants and products in the reaction are solids except the ‘oxygen, O, , which is a gas. Since the solids will be retained in the reaction vessel (a test tube) the only loss during the reaction is oxygen gas. The mass of oxygen may be obtained by weighing the test tube with the reaction mixture before and after heating; the difference in mass is the mass of oxygen lost. Having established the mass of ‘onygen in grams, the number of moles of oxygen may be calculated. The volume of oxygen is determined indirectly by using the generated gas to displace water from a closed flask into a beaker. The volume of water in the beaker is determined using a graduated cylinder. By equalizing the water levels inside the flask and in the beaker both before and after the gas is generated, the pressure inside the flask is set at the laboratory ambient pressure ‘The ambient pressure and temperature are determined by direct reading with a barometer and a thermometer, respectively. The barometer reading is corrected 10 0 C and the pressure of the oxygen gas alone (dry) is obtained by applying Dalton’s law. The oxygen gas volume is then corrected to STP. From the volume at STP and the number of moles, the volume per mole, or molar volume, is calculated, Chemists often indicate catalysts by writing the formula of the catalyst above the reaction arrow. In a similar way, the Greek letter A, indicating heat, is also often written over the arrow.EXPERIMENTS INVOLVING GASES PROCEDURE ———————— 1. Obtain a clean test tube (20 X 150 mm). Rinse the tube with distilled water, use a tissue to wipe the outside dry, and place the tube in a drying oven for a few minutes to evaporate the water from the inside of the ube. CAUTION: Do not use compressed air or al tissue to dry the inside of the tube. Potassium chlorate is a strong oxi ig agent and can react. explosively with orga matter such as grease or lint. 2. While the test tube cools, assemble the apparatus as shown in the drawing on page IV — 10. Carefully check all stoppers and tubing for possible leaks and correct any leaks. Leave the clamp open. Fill the flask with distilled water and, by blowing into the inlet tube where it would connect to the test tube, fill the delivery tube with water. Close the clamp. Add enough water to the beaker so that about an inch is present. 3. To the cool test tube, carefully add about 3 grams of the dry premixed potassium chlorate/manganese dioxide mixture. Use a clean metal spatula to handle the mixture and avoid getting ‘any dust on the upper part of the tube where it might contact the rubber stopper. See the CAUTION in paragraph 1. 4. Weigh the test tube and contents on an analytical balance. Record the mass. Be sure you record four decimal places. 5. Connect the test tube to the apparatus, clamping the tube near its top with the tube inclined away from the stopper at a slight angle so the reaction mixture will remain at the bottom of the tube. SEE APPARATUS BELOW. Now open the clamp on the delivery tube and wait a couple minutes. A small amount of water will flow from the delivery tube when the clamp is first opened; if the flow continues a leak is present and must be found and fixed before proceeding. 6. There should be about an inch or more of water in the beaker to cover the tip of the delivery tube. With the clamp still open raise the beaker until the level of water in the beaker is equal to that inside the flask. Hold the beaker at this level and w—8EXPERIMENTS INVOLVING GASES reclamp the delivery tube. The pressure inside the apparatus is now equal to the barometric pressure. 7. Discard any water in the beaker but do not dry it, Return it to its place under the delivery tube. Have your apparatus checked by the instructor before proceeding. CAUTION: Do not heat the test tube with the delivery tube clamped shut. Dangerous pressures can build up in the closed system: 8. Open the clamp on the delivery tube and, using a small clean (nonsmoky) flame, begin heating the KCIOYMnO, mixture at the upper edge of its contact with the test tube. Heat at a rate which maintains a steady moderate flow of water from the delivery tube into the beaker. If a white fog appears in the test tube or if the mixture begins to spatter, reduce the heating until the fogging or spattering stops. Fogging/spattering is an indication that the mixture is being overheated. Continue heating until about 300 mL of water has flowed into the beaker. Do not allow the level of water inside the flask to drop below the inside end of the delivery tube. 9. With the clamp open, allow the apparatus to cool to room temperature. While waiting, measure and record the temperature of the water in the beaker and read and record the barometric pressure and temperature. Correct the barometer reading for temperature using the table of corrections 10. When the apparatus has cooled to room temperature, with the clamp open and being careful not to allow the delivery tube tip to leave the water, raise either the flask or the beaker as necessary to equalize the water levels inside the flask and in the beaker. Hold the level and clamp the delivery tube. Use a graduated cylinder to measure the volume of water in the beaker. Record the volume on your data sheet 11, Weigh the coo! test tube on an analytical balance and record the mass. Be sure to record four decimal places. 12. Disassemble and empty the apparatus. Clean the test tube with water, rinsing any solid down the drain with water. Leave your working space neat and clean, v—9EXPERIMENTS INVOLVING GASES CALCULATIONS SS dl 2 Calculate the moles of O; from the weight loss of the mixture. Correct the volume of 0, to STP (0 C and 760.0 torr) and ary. 3. Calculate the molar volume in L/mole. 4. Using 22.414 L/mole as the accepted value, calculate your percent error. APPARATUS Chlorate Clamp test tube Inclined as shown WvV—10EXPERIMENT A: Name: DETERMINATION OF THE STANDARD MOLAR VOLUME OF OXYGEN Lab Day (circle): MT RF Lab Starting Hour: DATA Mass of test tube and KCIO,/MnO, mixture, before heating Mass of test tube and mixture, after heating: Mass of oxygen generated: Temperature of water: C_ | Barometer reading: torr Vapor pressure of water: torr Temperature at barometer: c Volume of water displaced: mt Barometer correction torr Instructor's initials before leaving lab: Corrected barometer reading: torr CALCULATIONS (Observe significant figures. Attach extra sheet if needed.) Moles of O,: Volume of O,, dry at STP: Molar volume of O, gas at STP: (Limole) Percent error in value: w—11EXPERIMENT A: QUESTIONS & PROBLEMS 1, Manganese dioxide is a catalyst for the reaction of potassium chlorate in this experiment. Explain what @ catalyst does. 2. How do you know that the pressure inside the test tubefflask assembly is equal to the laboratory Pressure as shown on the barometer? 3. Why must the clamp on the delivery tube be open while the apparatus cools and the pressures are equalized after the O, is generated? 4. Could this same experimental method be used to determine the molar volume of HCl gas (assuming a reaction which would generate the gas is available)? Give reasons for your answer. 5. In an experiment similar to this one, 0.628 g of methane gas (CH,) was generated. How many moles of gas is this? 6. What volume would you expect to find for the methane in 6. ifit is trapped over water at 20 C and 747.2 torr? (Methane is not very soluble in water.) W—12EXPERIMENT B: EXPERIMENTS INVOLVING GASES DETERMINATION OF THE MOLAR MASS OF CARBON DIOXIDE OBJECTIVES In this experiment you will: (1) use the concept of standard molar volume of a gas to calculate a gas's molar mass, o molecular weight; (2) use the gas laws to correct a gas volume from existing laboratory conditions to STP; 3) set up an apparatus to generate and dry carbon dioxide gas: (4) use a drying agent to remove water from a gas stream; (5) use gas density tables to determine a density for air at laboratory conditions; (© use density to obtain mass from volume and vice versa. BEFORE COMING TO LABORATORY To prepare for this lab, you should: 1, Read the sections in this manual dealing with measuring the volume, pressure, temperature, and mass of gases. Pay particular attention to the sample calculation on page Il — 5. 2. Use the index in your text to find sections in the text which correspond to the experiment and to the pertinent sections in the manual. Read these sections. 3. Read the experiment. High-light sentences or sections ‘which require you to take some action. Plan your approach tothe experiment. Make nots in the margins and ask about any material you don’t understand. Pay particular attention to any CAUTIONS in the ‘experiment INTRODUCTION ‘The molar volume concept, a8 applied to gases, allows the determination of the molar mass of a gas or vapor if the mass of gas which occupies a known volume at a known temperature and a known pressure can be determined. Assuming that a gas behaves nearly ideally, the molar mass, and thus the molecular weight, of the gas will be that mass of the gas which occupies 22.414 liters at 0 C and 760 mm Hg (STP). In this experiment a 250 mL. conical flask is used to contain the gas. The exact volume of the flask is obtained from the mass of water required to fill the flask and the known density of the water. The mass of dry air filling the flask is calculated from the volume of the flask and the density of air under ambient laboratory conditions. The ‘mass ofthe empty or evacuated flask is then determined by subtracting the mass of air in the flask from the mass of the flask filled with air. The mass of the “empry” flask is used to obtain the mass of gas which fills the flask. ‘The gas used is carbon dioxide gas generated by the reaction: CaCO, + 2HCI = CaCl, + H,0 + CO, ‘The carbon dioxide is wet as generated and must be dried by passing the gas over anhydrous calcium chloride in a ‘drying tube. Calcium chloride is a deliquescent salt which is relatively efficient at absorbing (reacting with) water; is sometimes used on dirt roads to keep dust at a minimum. It acts by removing moisture from the air, thus keeping the road surface damp and dust-free. WV—13EXPERIMENTS INVOLVING GASES PROCEDURE es 1. Fit a 250 mL conical flask with a stopper containing a glass or plastic tube which reaches nearly to the bottom of the flask (see page IV — 16 for an illustration of the apparatus). Clean only the flask with detergent and water, rinse with tap water several times, and finally rinse it with distilled water a couple times. Place the clean wet flask in the oven to dry. Once dry, the flask and stopper should be handled only with a Kimwipe® tissue to avoid fingerprints or dirt getting onto its surface. Set the flask on a clean piece of paper to avoid picking up moisture or dirt from the bench surface. 2. Using rubber tubing, connect the wet end of a CaCl,-filled rying tube to the air cock at your desk. Connect the dry end to the tube-fitted stopper Place the stopper loosely at a slight angle into the flask neck so that air can escape around it. Carefully and slowly open the air cock to obtain a gentle stream of air. Allow the air to flow through the flask for about 10 minutes, after which it can be assumed that the flask is filled with dry air at the laboratory temperature and pressure. 3. Using a tissue to avoid fingerprints, disconnect the rubber tubing at the stopper and gently seat the stopper in the flask neck. Weigh the air-filled flask/stopper on an analytical balance. Record the mass to four decimal places. 4. Set up the apparatus as shown on page IV — 16. The thistle tube should reach nearly to the bottom of the 500 mL generating flask. Place a small amount (about 30 grams) of marble chips (CaCO,) in the generating flask and add enough distilled water to just cover the lower end of the thistle tube. Check all connections for leaks. Check tubes to be sure no obstructions are present. The stopper in the weighed 250 mL Flask must be loosely fitted to allow gas to escape. 5. Carefully add dilute (6M) hydrochloric acid (HCI through the thistle tube. If liquid backs up the thistle tube, there must be an obstruction in the apparatus which is preventing the free flow of gas through it. Check that the stopper is loose in the 250 mL flask. Add acid at a rate which keeps the evolution of carbon dioxide gas steady and fairly rapid. Generate gas for about 20 minutes, occasionally checking the rate by pinching the delivery tube and observing the rate at which liquid rises WV—14EXPERIMENTS INVOLVING GASES in the thistle tube. . While the carbon dioxide gas is flowing into and filling the 250 mL flask, lay a thermometer on your bench top and record the temperature as the temperature of the gas. Read the barometer and its temperature and record the values, Calculate the corrected barometric pressure. Obtain the air density from a table of air densities versus temperature and pressure. . Disconnect the flask and stopper from the delivery tube, gently push the stopper into place in the flask neck, and weigh the flask and stopper on an analytical balance. Do not delay weighing the flask; the gas is kept in the flask only by its slowness in escaping through the tube. If a long delay occurs before weighing, some air will move into the flask and some carbon dioxide will escape. Record the mass to four decimal places. . Remove the stopper from the 250 mL flask and fill the flask to the rim with distilled water. Replace the stopper, seating it carefully into the water so as to avoid trapping any air bubbles under the stopper or in the tube through the stopper. Seat the stopper to the same depth used for the air and the carbon dioxide. If there are bubbles inside the flask or tube, try again. [Dry the outside of the flask and stopper and| lweigh the assembly on a toploading balance.| Do not attempt to weigh the filled flask and| stopper on an analytical balance; the mass Record the mass. Place a thermometer into the water and record the temperature of the water. Obtain the density of water from a table of water densities versus temperature. . Disconnect the apparatus and empty and clean the flasks. Leave them rinsed with distilled water. Dispose of the remains of the marble chips and acid in the designated waste container, not in the sink, Clean up your work space. WV—15EXPERIMENTS INVOLVING GASES CALCULATIONS 1. From the mass of water used to fill the flask and the density of the water, calculate the volume of the flask. 2. Correct the volume of the flask (and thus the volume of CO;) to STP. 3. From the volume of the flask and the density of air, calculate the mass of air contained in the flask and, from it, the “empty” mass of the flask. 4. Calculate the mass of CO, contained in the flask. Use this mass, the STP volume of the gas, and the standard molar volume to calculate the molar mass of CO, in grams per mole. 5. Look up or calculate the correct molar mass for CO, and calculate the percent error in your result. APPARATUS =) Thistle a Calcium chloride drying tube (Wet end) Stopper must be kept loose Marble chips and water V—16EXPERIMENT B: Name: DETERMINATION OF THE MOLAR MASS | Lab Day (circle): M T W R F OF CARBON DIOXIDE Lab Starting Hour: DATA Mass of flask/stopper filled with air: 9 Mass of flask/stopper filled with carbon dioxide: 9 Mass of flask/stopper filled with water (toploading balance): g ‘Temperature of air & CO,! C__| Barometer reading: torr ‘Temperature of water: c Correction: torr ‘Temperature at barometer: C | Corrected pressure: torr Density of water: gimL__| Density dry air (above T & P): g/m Instructor's initials before leaving lab: CALCULATIONS (Observe significant figures. Attach sheet if necessary. Show set-ups with units.) Volume of flask/stopper: (mL) Volume of CO, at STP: (mL) Mass of air in flask/stopper: (g) Mass of empty flask/stopper: (9) Mass of CO, in flask/stopper: (9) Molar mass of CO,(STP): (g/mol) Percent error in molar mass: Ww-17EXPERIMENT B: QUESTIONS & PROBLEMS, [7. How does CaCl, act to remove water from a gas? 2. How is it possible to use a mass for the flask/stopper plus water to only one or two decimal places when all the other masses are to four decimal places? 3. The mass of water in this experiment is obtained by subtracting the mass of the flask/stopper/air from the mass of the flask/stopper/water. Show algebraically that this method incurs an error. Estimate the size of the error. 4, Could this same experiment be used to determine the molar volume of HCI gas (assuming a reaction is available to generate the gas)? Explain your answer. 5. In an experiment 326 mL of dry N, gas are generated at 752.0 torr and 17 C. What is the volume of gas. at STP? 6 How many grams of N, gas were generated in 5.7 WV—18