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Gases Common gases Molecular compounds: HCN, HCl, H2S, CO2, CO, CH4, N2O, NO2, NH3, SO2 Nonmetals: N2, F2, O2, H2, He, Ne, Ar, Kr, Xe Characteristics Small particles relatively far apart Indefinite shape and volume High expansion High compressibility Considered a fluid As temperature increases, gases expand High diffusion Four factors That Describe the State of a Gas 1. Volume (V) - measured in L, ml, cm3, m3 2. Amount of gas ( n) – measured in moles moles = mass of sample/molar mass of sample 3. Temperature (T) – measured in Kelvin ; remember K = ºC + 273 4. Pressure ( P) – measured in Pa, kPa, torr, atm, mm Hg, bar Pressure Pressure = force area defined as the force per unit area in simple terms, molecules collide with container walls AIR PRESSURE A manometer is used to measure the of a gas in a container; can be open or closed pressure Hg HEIGHT DIFFERENCE Atmospheric Pressure • pressure on the surface of the earth exerted by the gases of the atmosphere • measured with a barometer vacuum air pressure • • at sea level, atmospheric pressure = 760 mm Hg most abundant gases in the environment: N2 >O2 > CO2 > mercury (Hg) Pressure Units SI Unit – Pascal (Pa) Other units and how they relate: 1atm(bar) = 760 mm Hg (torr)= 101.3 kPa Example 1 Convert 875 mm Hg into atm? into torr? into kPa? Gas Laws 1. Boyle’s Law (pressure-volume) Volume of a gas is inversely proportional to pressure at constant temperature and moles; as one goes up, the other goes down PV = constant Thus V1 P1 = V2 P2 Example 2 20.5 L of nitrogen at 25ºC and 742 torr are compressed to 9.80 atm at constant temperature and moles. What is the new volume? 2. Charles’ Law (volume –temperature) Volume of a gas is directly proportional with absolute temperature (Kelvin) at constant pressure and moles; as one goes up, the other does as well V /T = constant Thus V1 = V2 T1 T2 Example 3 What would the final volume be if 247 ml of gas at 22ºC is heated to 98 ºC, if the pressure is held constant? 3. Gay – Lussac’s (Amonton’s) Law Pressure of a gas is directly proportional to absolute temperature(Kelvin) at constant volume and moles P/T = constant Thus P1 = P2 T1 T2 Example 4 A deodorant can have a volume of 175 ml and a pressure of 3.8 atm at 22 ºC. What would the pressure be if the can was heated to 100. ºC 4. Avogadro’s Law Equal volumes of gases at same temperature and pressure contain equal numbers of moles (molecules) Number of gas molecules are directly proportional to volume V / n = constant Thus V1 = V2 n1 n2 0ºC and 1 atm : Standard Temperature and Pressure (STP) molar volume 1 mole of gas at STP contain 22.4 L and thus 6.02 x 1023 molecules Helium He 22.4 L 1 atm 0º C 4.00 g 6.02 x 1023 molecules Nitrogen N2 22.4 L 1 atm 0º C 28.0 g 6.02 x 1023 molecules Methane CH4 22.4 L 1 atm 0º C 16.0 g 6.02 x 1023 molecules 5. Gay-Lussac also observed the Law of Combining Volumes At a given temperature and pressure, volumes of gases react in whole number ratios Coefficient in a balanced chemical equation = moles and now volume (only when temperature and pressure are constant) 2 H2(g) + O2(g) 2 H2O (g) 100 ml 50 ml 100 ml Example 5 What volume of NO will be produced by 1.38 L of oxygen when both volumes are measured at the same temperature and pressure? 2 NO(g) + O 2(g) --> 2 NO (g) 6. Combined Gas Law – when all variables are changing but moles stays constant V1 P1 = V2 P2 T1 T2 • Cancel (i.e., ignore) any property that is not changing. (Assume anything not explicitly mentioned in the problem is not changing.) • Units must be the same on both sides of the equal sign • Temperatures must be absolute (Kelvin). Example 6 A sample of gas has a volume of 4.18 L at 29 ºC and 732 torr. What would its volume be at 24.8 ºC and 756 torr? 7. Ideal Gas Law –used to describe an ideal gas “NOW”, not when variables are changing PV = nRT Ideal gas- hypothetical gas that is calculated using the above equation; actually very similar to real gas behavior when close to room temperature and low pressures (1atm and less) Assume gases obey all gas laws stated above unless otherwise stated Ideal gas law constant(R) - changes depending on the units Choose a value of R that has exactly the same units as the numbers you are given in the problem. If this is not possible, you must convert the units from the problem to units that agree with your R value. Manipulation of R – to calculate the constant, remember at O·C and 1 atm, 1 mole of any gas is 22.4 L .08206 L· atm/mol· K or 62.4 L ·mmHg/ mol·K “ most common” Example 7 A 47.3 L container containing 1.62 mol of He is heated until the pressure reached 1.85 atm. What is the temperature? Example 8 How many grams of oxygen gas in a 10.0 L container can exert a pressure of 712 mm Hg at a temperature of 25.0ºC? 8. Other Calculations involving the ideal gas law Determining Molar Mass (M) PV = nRT PV = mRT M Determining Density (D) SO M = mRT M= DRT SO PV P As molar mass increases, density increases As molar mass increases, pressure decreases As molar mass increases, temperature increases M= mRT PV D= MP RT Example 9 When 4.93 g of carbon tetrachloride gas are in a 1.00 L container at 400.0 K, the gas exerts a pressure of 800.0 mm Hg . What is the molar mass of carbon tetrachloride? Example 10 The density of an unknown gas is 1.23 grams per liter at STP. Calculate its molar mass Stoichiometry of Reactions Involving Gases Use PV=nRT to get any and all gases to moles and then solve the problem using stoichiometry Could also use molar volume if the gas was measured at STP Example 11 How many grams of MnO2 are required to produce 1.200 L of Cl2 gas at 1.00 atm and 200. C? MnO2 + 2 Cl-1 + 4 H+1 --> Mn+2 + Cl2 + 2 H2O Example 12 Calcium oxide is produced by the thermal decomposition of calcium carbonate. Calculate the volume of carbon dioxide at STP produced from the decomposition of 152g calcium carbonate by the reaction. Write it yourself! Dalton’s Law of Partial Pressures Mixture of gas = blend of gases each retaining their individual properties Each exerts a specific pressure(called partial pressure) as it would by itself Total Pressure of gas mixture = sum of the partial pressures of each individual gas PT = P1 + P2 + P3 …. • The total moles of a gas in a mixture can be found using the mole fraction(X) MOLE FRACTION = moles of individual gas/total moles of gas in a miture X= n1 nT Since moles and pressure are proportional P1 = X OR P1 = PTX PT Example 13 The partial pressure of nitrogen in air is 592 torr. Air pressure is 752 torr. a. What is the mole fraction of nitrogen? b. What is the partial pressure of nitrogen if the container holding the air is compressed to 5.25 atm? • • Example14 A 12.0 L tank of gas has a temperature of 30.0°C and a total pressure of 1.75 atm. If the partial pressure of oxygen in the tank is 0.350 atm, how many moles of oxygen are in the tank? How many total moles of gas are in the tank? Collecting Gas Over Water gas being collected filled with water, initially collected gas (w/H2O vapor, too) gas from reaction H2O levels even before reaction during reaction reaction complete When collecting gas over water, water vapor will mix with the collected gas. Water vapor has a pressure and must be accounted for when determining the pressure of the gas collected. Its dependent on temperature. PT = Pgas + Pwater PT at various temperatures found in the Appendix Example 15 2 KClO3 --> 2 KCl + 3 O2. The oxygen was collected by water displacement at 22 ºC at a total pressure of 754 torr. The volume of the gas collected was .650 L and the vapor pressure for water at 22 ºC is 21 torr. Calculate the partial pressure of the oxygen gas collected and the mass of KClO3 in the sample that decomposed. Kinetic Molecular Theory 1. Gas particles are in constant random motion. 2. The volume of the gas particles is negligible compared to the volume of the container. GASES HAVE NO VOLUME! 3. The attractive and repulsive forces between molecules are negligible. GASES HAVE NO ATTRACTIONS/REPULSIONS! 4. Collisions of gas molecules are ELASTIC. NO KINETIC ENERGY IS LOST! 5. The Average Kinetic Energy of gas molecules is directly proportional to KELVIN temperatures At a given temperature, the gas particles of Sample A have the same KE as the gas particles of Sample B. Average Speed Molecules at the same temperature have the same average KE and same average speed BUT individual molecules move at varying speeds KEparticle = ½ mv2 m= mass of molecule 1J = 1 kg· m2/s2 v= speed of the molecule Root Mean Square Speed (RMS) ( u) • The average speed of a molecule possessing average KE As average temperature increases, average KE and average speed increases R = 8.3125 J/K· mol Urms = 3RT/M M= molar mass (kg/mol) T = Kelvin Speed is directly related to absolute temperature but inversely related to molar mass The lower the molar mass, the higher the RMS A gas mixture consisting of He and Xe are at the same temperature SO They have greater, same, lower average KE They have greater, same, lower average speed Example 16 Calculate the RMS of carbon dioxide at 25ºC Graham’s Law The lighter the molecules, the faster they move; the heavier the particles, the slower they move • Effusion – escape of a gas through a small hole or pore Diffusion- spread of 1 substance throughout a second substance or space from high concentration to low Rates r1 = M 2 r2 M 1 M= molar mass We usually place the lighter mass as gas 1 If the ratio is greater than 1, gas 1 is effusing faster than gas 2 effusion rate is faster for lighter molecules; same for diffusion diffusion is slightly slower due to collisions of molecules Example 17 Calculate the ratio of effusion rates of molecules from SO2 to NO2 Real gases deviate from ideal gas behavior • All real gases, to some degree, behave differently from ideal gas behavior because particles of a real gas occupy space and exert attractive forces. • The deviations are most recognizable when gases are at extremely low temperatures or at very high pressures ( > 10 atm) • This is due to the small KE of the particles and the particles will be closer together. Real gases (Noble gases and diatomic molecules) ALWAYS show ideal gas behavior The more polar a molecules is, the greater the deviation because of the greater attractive forces- See van der Waal’s equation Use of van der Waals Equation High pressure – molecules are closer together increases the likelihood of attraction Low temperature- movement decreases increases the likelihood of attraction Amount of deviation depends on the type of gas The constants a and b are unique for each gas! (See the book for them) a (molecular attraction) & b( molecular volume) Example 18 Calculate the pressure exerted by .3000 mol He in a .2000L container at -25 °C A. using the ideal gas law equation B. using the vander waals equation- constants are taken from the book within the chapter