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Gases Chapter 10 Copyright © The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Elements that exist as gases at 250C and 1 atmosphere 5.1 5.1 Physical Characteristics of Gases • Gases assume the volume and shape of their containers. • Gases are the most compressible state of matter. • Gases will mix evenly and completely when confined to the same container. • Gases have much lower densities than liquids and solids. 5.1 Chemistry in Action: Scuba Diving and the Gas Laws P Depth (ft) Pressure (atm) 0 1 33 2 66 3 V 5.6 Chemistry in Action: Super Cold Atoms Gaseous Rb Atoms 1.7 x 10-7 K Bose-Einstein Condensate Pressure • Pressure is the amount of force applied to an area. 2009, Prentice-Hall, Inc. Force Pressure = Area (force = mass x acceleration) Units of Pressure Barometer 5.2 Manometers Used to Measure Gas Pressures 5.2 Kinetic Molecular Theory of Gases KE = ½ mu2 5.7 Kinetic Molecular Theory of Gases and the Particulate Nature of Matter • What is the relationship between pressure and volume? • As the volume decreases the pressure ___ • Mathematically: • Experimentally 5.7 P a 1/V P x V = constant P1 x V1 = P2 x V2 Constant temperature Constant amount of gas 5.3 A sample of chlorine gas occupies a volume of 946 mL at a pressure of 726 mmHg. What is the pressure of the gas (in mmHg) if the volume is reduced at constant temperature to 154 mL? 5.3 A sample of chlorine gas occupies a volume of 946 mL at a pressure of 726 mmHg. What is the pressure of the gas (in mmHg) if the volume is reduced at constant temperature to 154 mL? 5.3 Kinetic Molecular Theory of Gases and the Particulate Nature of Matter • What is the relationship between temperature and volume? • As the temperature decreases the volume ___ • Mathematically: V a T • Experimentally 5.7 • The volume of a fixed amount of gas at constant pressure is directly proportional to its absolute temperature. • i.e., 2009, Prentice-Hall, Inc. Variation of gas volume with temperature at constant pressure. VaT V = constant x T V1/T1 = V2 /T2 Temperature must be in Kelvin T (K) = t (0C) + 273.15 5.3 A sample of carbon monoxide gas occupies 3.20 L at 125 0C. At what temperature will the gas occupy a volume of 1.54 L if the pressure remains constant? 5.3 Kinetic Molecular Theory of Gases and the Particulate Nature of Matter • What is the relationship between the number of moles of gas and the volume? • As the number of moles of gas increases the volume ___ • Mathematically: • Experimentally 5.7 Avogadro’s Law Va V= Constant temperature Constant pressure 5.3 Avogadro's Hypothesis Gay -Lussac's Law of Combining Gas Volumes 5.3 Ammonia burns in oxygen to form nitric oxide (NO) and water vapor. How many volumes of NO are obtained from one volume of ammonia at the same temperature and pressure? 5.3 Ideal Gas Equation Boyle’s law: Charles’ law: Avogadro’s law: Va V= R is the gas constant 5.4 Ideal-Gas Equation The constant of proportionality is known as R, the gas constant. 2009, Prentice-Hall, Inc. Calculate the volume of a 0.500 mole sample of Helium gas at 1.00 atm pressure and 298 K 5.4 Argon is an inert gas used in lightbulbs to retard the vaporization of the filament. A certain lightbulb containing argon at 1.20 atm and 18 0C is heated to 85 0C at constant volume. What is the final pressure of argon in the lightbulb (in atm)? 5.4 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 5.3 The conditions 0 0C and 1 atm are called standard temperature and pressure (STP). Experiments show that at STP, 1 mole of an ideal gas occupies 22.414 L. PV = nRT (1 atm)(22.414L) PV R= = nT (1 mol)(273.15 K) R= 5.4 What is the volume (in liters) occupied by 49.8 g of HCl at STP? T = 0 0C = 273.15 K 5.4 Density (d) Calculations PM m d= = V RT m is the mass of the gas in g M is the molar mass of the gas Molar Mass (M ) of a Gaseous Substance dRT M= P d is the density of the gas in g/L 5.4 A 2.10-L vessel contains 4.65 g of a gas at 1.00 atm and 27.0 0C. What is the molar mass of the gas? M= M= 5.4 Gas Stoichiometry What is the volume of CO2 produced at 37 0C and 1.00 atm when 5.60 g of glucose are used up in the reaction: C6H12O6 (s) + 6O2 (g) g C6H12O6 mol C6H12O6 6CO2 (g) + 6H2O (l) mol CO2 V CO2 Dalton’s Law of Partial Pressures V and T are constant P1 P2 Ptotal = P1 + P2 5.6 Consider a case in which two gases, A and B, are in a container of volume V. nART PA = V nA is the number of moles of A nBRT PB = V nB is the number of moles of B PT = PA + PB PA = XA PT nA XA = nA + nB nB XB = nA + nB PB = XB PT Pi = Xi PT mole fraction (Xi) = ni nT 5.6 A sample of natural gas contains 8.24 moles of CH4, 0.421 moles of C2H6, and 0.116 moles of C3H8. If the total pressure of the gases is 1.37 atm, what is the partial pressure of propane (C3H8)? Pi = Xi PT PT = 1.37 atm 0.116 Xpropane = 8.24 + 0.421 + 0.116 = 0.0132 Ppropane = 0.0132 x 1.37 atm = 0.0181 atm 5.6 Densities of Gases If we divide both sides of the ideal-gas equation by V and by RT, we get n P = V RT 2009, Prentice-Hall, Inc. Gas diffusion is the gradual mixing of molecules of one gas with molecules of another by virtue of their kinetic properties. r1 r2 = M2 M1 NH4Cl NH3 17 g/mol HCl 36 g/mol 5.7 Densities of Gases • Mass volume = density • So, m P d= = V RT Note: One only needs to know the molecular mass, the pressure, and the temperature to calculate the density of a gas. 2009, Prentice-Hall, Inc. Molecular Mass We can manipulate the density equation to enable us to find the molecular mass of a gas: P d= RT Becomes dRT = P 2009, Prentice-Hall, Inc. Partial Pressures • When one collects a gas over water, there is water vapor mixed in with the gas. • To find only the pressure of the desired gas, one must subtract the vapor pressure of water from the total pressure. 2009, Prentice-Hall, Inc. Bottle full of oxygen gas and water vapor 2KClO3 (s) 2KCl (s) + 3O2 (g) PT = PO2 + PH2 O 5.6 Dalton’s Law of Partial Pressures • The total pressure of a mixture of gases equals the sum of the pressures that each would exert if it were present alone. • In other words, Ptotal = P1 + P2 + P3 + … 2009, Prentice-Hall, Inc. 5.6 Densities of Gases • We know that – moles molecular mass = mass n=m • So multiplying both sides by the molecular mass ( ) gives m P = V RT 2009, Prentice-Hall, Inc. Effusion Effusion is the escape of gas molecules through a tiny hole into an evacuated space. 2009, Prentice-Hall, Inc. Effusion The difference in the rates of effusion for helium and nitrogen, for example, explains a helium balloon would deflate faster. 2009, Prentice-Hall, Inc. Gas effusion is the is the process by which gas under pressure escapes from one compartment of a container to another by passing through a small opening. r1 r2 = t2 t1 = M2 M1 Nickel forms a gaseous compound of the formula Ni(CO)x What is the value of x given that under the same conditions methane (CH4) effuses 3.3 times faster than the compound? r1 = 3.3 x r2 5.7 Diffusion Diffusion is the spread of one substance throughout a space or throughout a second substance. 2009, Prentice-Hall, Inc. Graham's Law KE1 = KE2 1/2 m1v12 = m1 m2 = 1/2 2 m v v 22 2 2 v 12 2 v = 2 2 v m 1 1 m2 = v2 v1 2009, Prentice-Hall, Inc. Apparatus for studying molecular speed distribution 5.7 Main Tenets of KineticMolecular Theory Energy can be transferred between molecules during collisions, but the average kinetic energy of the molecules does not change with time, as long as the temperature of the gas remains constant. 2009, Prentice-Hall, Inc. Main Tenets of KineticMolecular Theory The average kinetic energy of the molecules is proportional to the absolute temperature. 2009, Prentice-Hall, Inc. The distribution of speeds of three different gases at the same temperature The distribution of speeds for nitrogen gas molecules at three different temperatures urms = M 3RT 5.7 Deviations from Ideal Behavior The assumptions made in the kinetic-molecular model (negligible volume of gas molecules themselves, no attractive forces between gas molecules, etc.) break down at high pressure and/or low temperature. 2009, Prentice-Hall, Inc. Corrections for Nonideal Behavior • The ideal-gas equation can be adjusted to take these deviations from ideal behavior into account. • The corrected ideal-gas equation is known as the van der Waals equation. 2009, Prentice-Hall, Inc. Effect of intermolecular forces on the pressure exerted by a gas. 5.8 Van der Waals equation nonideal gas 2 an ( P + V2 ) (V – nb) = nRT } } corrected pressure corrected volume 5.8 Real Gases In the real world, the behavior of gases only conforms to the idealgas equation at relatively high temperature and low pressure. 2009, Prentice-Hall, Inc. Real Gases Even the same gas will show wildly different behavior under high pressure at different temperatures. 2009, Prentice-Hall, Inc. Deviations from Ideal Behavior 1 mole of ideal gas PV = nRT PV = 1.0 n= RT Repulsive Forces Attractive Forces 5.8