9 Air ina tire exerts pressure. A partially filled balloon will expand if it is placed over a hot radiator. In marked contrast to solids and liquids, gas volumes change noticeably with small changes in pressure and temperature. These changes were studied by experimenting with actual gases and the relations ‘obtained were reduced to equations which defined the behavior of gases. These gas laws are valid only for an ideal gas* which does not actually exist. However, they give good approxi- mations in most situations for real gases. Gas Laws 9:1 Gas Pressure What is gas pressure? As gas molecules hit the walls of a container, the particles exert a force on the container. It is the number of collisions and the force of the collisions that cause gas pressure. Air pressure at sea level has been used as a scientific standard of pressure. However, this pressure changes with changing weather conditions. The standard is now defined in pascals which represent force per unit area. One pas- cal (Pa) is the pressure of 1 newton per square meter (N/m’). Normal air pressure at sea level is 101 325 Pa or 101.325 kilopascals (kPa). A barometer is used to measure atmospheric pressure. Most ba- rometers are calibrated in millimeters of mercury (mm Hg). For con- verting units, 101.325 kPa equal 760 mm or 1 kPa = 7.50 mm Hg. 9:2 Boyle’s Law If the pressure on an ideal gas in a confined container is increased, the volume decreases. When the pressure is doubled, the new gas + An ideal gas is one composed of particles with no attractive forces and no volume, 8788 Gas Laws volume is half the original gas volume. If the pressure is decreased to half the original pressure, the new volume is double the old volume. Boyle's law is the volume of an enclosed gas varies inversely as the pres- sure, if the temperature remains constant. Boyle's law states that volume and pressure vary inversely. As one becomes larger, the other becomes smaller. The preferred volume unit is cubic meters (m3). However cubic decimeters (dm:), cubic centimeters (cm), and liters (L), are also used. The following graph illustrates the relationship of pressure and vol- ume as expressed by Boyle's Law. Pressure increases to the right along the horizontal axis. Volume increases upward on the vertical axis. ™ Volume of gas sample Figure 9-1 Pressure (P) {at constant T) Our primary interest in solving Boyle’s law problems is to find a new volume when the original volume and the change in pressure are known. The change in pressure can be represented by a pressure ratio. The calculation of a new volume of a gas after a change in pressure at a constant temperature is where V, is the initial volume and P, is the initial pressure. The given values can be substituted into the equation or the changes in the gas volume can be visualized using Boyle’s law. Mentally determine whether the new volume will be larger or smaller and arrange the pressure ratio accordingly. If the new volume will be larger, multiply by a ratio that is greater than 1; if smaller, multiply by a ratio less than 1. In summary: A pressure increase decreases the volume, which means the pres- sure ratio should be less than 1. A pressure decrease increases the volume, which means the pres- sure ratio should be greater than 1.Gas Laws 89 Se To calculate a new pressure when the old pressure and the volume change are known, use the relationship: new pressure = old pressure X volume ratio The volume and pressure vary inversely. Example 4———___———————— If 400 cm? of oxygen are collected at a pressure of 9.80 kPa what volume will the gas occupy if the pressure is changed to 9.40 kPa? Solving Process: The pressure decreases from 9.80 to 9.40 kPa. The volume should increase according to Boyle’s law. To have a volume increase, the pressure ratio must be greater than 1. The pressure ratio is 9.80 kPa 9.40 kPa In calculations, use the relationship: new volume = old volume x pressure ratio 3 400 cm‘ = 417 m3 Example 2——— $$ What is the volume of hydrogen at a pressure of 106 kPa if 200 cm of the hydrogen were collected at a pressure of 100 kPa? Solving Process: The pressure is increased from 100 to 106 kPa. Hence, the volume must decrease. The pressure ratio will be less than 1. 100 kPa 106 kPa Therefore 200 cm? | 100 $8 _ 189 cm? 106 kPa Example 3. Calculate the pressure of a gas which occupies a volume of 400 cm’, if at a pressure of 95 kPa, it occupies a volume of 200 cms, Solving Process: The volume decreases from 200 cm® to 100 cm’. The pressure must increase, so the volume ratio must be greater than 1, or 200 cm? 100 cm 95 kPa | 200.cm* 100 cane 190 kPa90 Gas Laws Problems vd 2 a. - 6. et The unit millimeter of mercury is used to measure blood pressure. As the blood is forced from the heart, the pressure is about 120.0 mm Hg. Before the next contraction, the pressure drops to about 80.0 mm Hg. Convert these pressures to pascals. Correct the following gas volumes from the initial conditions to the new conditions (assume the temperature remains constant): a. 100.0cm? oxygen at 10.50kPa to 9.91 kPa b. 50.0cm3 hydrogen at 97.3 kPa to 101000 Pa c. 500.0 cm3 sulfur dioxide at 95.6 kPa to 101.3kPa d. 150.0 cm3 nitrogen at 101.30kPa to 120.0kPa e. 2.00 m3 nitrogen at 158.0 kPa to 109.0kPa f. 1.50dm} neon at 98.2kPa to 150kPa A flask containing 90.0 cm} of hydrogen was collected under a pres- sure of 97.5 kilopascals. At what pressure would the volume be 70.0 cm}, assuming the temperature is kept constant? A gas has a volume of 275cm3 when measured at a pressure of 9.80 x 10* Pa. If the temperature is not changed, what would be the volume of gas at standard pressure? A gas has a volume of 50.0 m? at standard pressure. Assuming no temperature change, what volume will the gas occupy a. if the pressure is doubled? b. if the pressure is tripled? c. if the original pressure is cut in half? What is the volume occupied by 10.0 dm} of gas at standard pres- sure after it has been compressed at constant temperature to 500.0 kPa? A gas is confined in a cylinder with a movable piston at one end. When the volume of the cylinder is 760 cm: the pressure of the gas is 125.0 pascals. When the cylinder volume is reduced to 450 cm, what is the pressure? 9:3 Dalton’s Law of Partial Pressure If a gas is a mixture of two or more gases, each gas exerts a partial pressure independently of the other gases present. The partial pressure of agas in a mixture is the pressure that the gas would exert if it were the only gas in the container. The total pressure is equal to the sum of the individual gas pressures. Dalton’s law of partial pressures can be stated as the sum of the partial pressures of a mixture of gases is the total pressure exerted by the enclosed gases.Gas Laws 94 EE This statement means that each gas exerts the same pressure it would exert if it alone were present at the same temperature. In the chemistry laboratory, gases (such as oxygen, nitrogen, and hydrogen) are collected by water displacement. These gases bubble through water as they are collected. As a result, water vapor molecules become part of the total volume of the wet gas. Water vapor molecules exert a pressure along with the collected gas. Any temperature increase causes the water molecules to move faster and hit the sides of the container with more force. Water vapor pressure increases, as temperature increases. Since gas pressure is caused by the collision of gas particles with the walls of the container, the total pressure in a container is due to the total number of particles. The pressure of the dry gas can be found only by deducting the pressure due to water molecules. Look at Table 9-1 and note that the vapor pressure depends upon the temperature. The warmer the gas, the greater the pressure of the water vapor. Table 9-1 Vapor Pressure of Water Temperature Pressure Temperature Pressure (°C) (kPa) (°C) (kPa) o 06 26 34 5 0.9 27 36 8 1 28 38 10 1.2 29 4.0 12 14 30 42 14 16 35 5.6 16 1.8 40 74 18 24 50 12.3 20 23 60 19.9 at 25 70 31.2 22 26 80 47.3 23 28 90 70.4 24 3.0 100 101.3 25 3.2 200 1554.4 Assume that the atmospheric pressure is 98.0 kPa and the enclosed gas has been adjusted to atmospheric pressure. The pressure is a com- bination of the dry gas pressure and the water vapor pressure. atmospheric pressure = pressure of dry gas + pressure of water vapor pressure of dry gas = atmospheric pressure — pressure of water vapor At 10°C: pressure of dry gas = 98.0 — 1.2 = 96.8kPa At 20°C: pressure of dry gas = 98.0 — 2.3 = 95.7kPa