Chapter 1 GASES

1.1 Pressure One of the most important properties characterizing a gas is its pressure. Pressure is defined as the force exerted per unit area. Atmospheric pressure is the force exerted by the atmosphere on the Earths surface. A common device used to measure atmospheric pressure is the barometer. The barometer was invented in 1643 by Evangelista Torricelli (16081647). Torricelli, who was a student of Galileo, was presented with the problem of why water could not raise more than 32 feet with a suction pump. Galileo explained the rise of water up a pipe by invoking the statement nature abhors a vacuum. When a pump created a vacuum, Galileo believed water rose to fill the void created, but somehow there was a limit of approximately 32 feet. Torricelli reasoned correctly that the height to which water could be pumped was due to atmospheric pressure. In his study of the pump problem, Torricelli took a sealed tube approximately four feet in length and filled it with mercury. He inverted the tube in a pool of mercury. Torricelli noticed that the mercury in the tube fell, creating a vacuum at the top of the tube. The final height of the mercury in the tube was roughly 28 inches. Because mercury has 13.5 times the density of water, Torricelli proposed that water should rise about 13.5 _ 28 inches or about 32 feet. Torricelli reasoned that atmospheric pressure placed a limit on how high a liquid could raise in the tube. His inverted mercury-filled tube was the first barometer (Figure 9.1). Many units are used to express pressure. Because pressure is defined as force per unit area, a common unit used in the United States is pounds per square inch. This unit is commonly used for tire inflation pressure. The atmospheric pressure at sea level is about 14.7 pounds per square inch. In the metric system, the basic unit for force is the newton, abbreviated N, and area is measured in squared meters, m2. Therefore, the metric unit for pressure is newtons per squared meter, N/m2. A N/m2 is also known as a pascal, abbreviated Pa. As we have seen, atmospheric pressure can also be expressed by measuring the height of mercury in a barometer. This measurement is given in inches in the United States and is how atmospheric pressure is reported in daily weather reports. In the metric system, the height of mercury is given in millimeters of mercury. A common unit used by chemists to express pressure is atmospheres. One atmosphere is equal to normal

atmospheric pressure at sea level. The various units for pressure and the value of standard atmospheric pressure are summarized in Table 1.2. The values in column three of Table 1.2 are atmospheric pressure at sea level. At the top of Mt. Everest, the atmospheric pressure is only one-fourth of that at sea level. The pressure in Denver is about three fourths of that at sea level. While changes in elevation have pronounced effects on atmospheric pressure, temperature and moisture also affect atmospheric pressure. Changes in the moisture and temperature of air masses produce high and low pressure systems that move across the continent dictating our weather. Pressure increases underwater because the water pressure adds to the atmospheric pressure. Ten meters (33 feet) of water is equivalent to 1 atmosphere of pressure. Table 1.1. Composition of Earths Atmosphere by Volume

Figure 1.1 In a mercury thermometer, atmospheric pressure, P, forces mercury to rise in the tube to a height of approximately 30 inches

We can understand how atmospheric pressure is just the weight of the atmosphere pushing down on the Earths surface, but how can we apply the basic definition of pressure to a confined gas? To expand our concept of pressure and provide a basic framework for understanding the behavior of gases, we use a simple model for a confined gas. This model is known as the kinetic molecular theory. The kinetic molecular theory states: 1. A gas consists of small particles, either individual atoms or molecules, moving around randomly. 2. The total volume of the gas particles is so small compared to the total volume the gas occupies that we can consider the total particle volume to be zero. This means that a gas consists almost entirely of empty space. 3. The gas particles act independently of one another. A particle is not attracted to nor repelled from any other particle. 4. Collision between gas particles and between gas particles and the walls of the container are elastic. This means that the total kinetic energy of the gas particles is constant as long as the temperature is constant. 5. The average kinetic energy of the gas particles is directly proportional to the absolute temperature of the gas. The kinetic molecular theory is used throughout the discussion of gases and should become clearer as examples are used that illustrate this theory. First, the kinetic molecular theory is used to explain pressure. We can use a sealed syringe as our container and assume it contains a volume of air. To simplify our discussion, we will also assume air consists of 80% nitrogen and 20% oxygen (Figure 1.2). The nitrogen and oxygen molecules move randomly in the barrel of the syringe. The molecules collide with the walls of the syringe barrel and the face of the syringes plunger (as well as with each other). The collisions exert a constant force on the inside surface area of the walls of the syringe barrel. The force exerted per unit area of the syringes internal surface is the pressure of the gas. Because the molecules move randomly throughout the syringe barrel, the pressure is the same throughout the syringe. If we assume the pressure outside the syringe is 1 atmosphere and that the plunger is not moving, then the pressure inside the syringe must also be 1 atmosphere. So the pressure of a confined gas is nothing more than the force caused by the constant bombardment of the gas particles on the sides of the container.

Figure 1.2 Syringe filled with air that is assumed to be 80% nitrogen and 20% oxygen Table 1.2 Pressure Units and Values for Standard Atmospheric Pressure

1.2 The Gas Laws Continuing to use a syringe as a container, the basic gas laws can be explained. These laws apply to what is referred to as an ideal or perfect gas. An ideal or perfect gas can be thought of as a gas that conforms to the kinetic molecular theory. In reality, gas molecules do have volume and exert forces on each other. Under normal conditions of temperature and pressure, though, the kinetic molecular theory explains the behavior of gases quite well. It is only when a gas is at very low temperatures and/or under extremely high pressure that a gas no longer behaves ideally. The definition of pressure assumed the volume of the air contained in the syringe was constant. What would happen if the plunger is pushed while making sure that the opening remained sealed (Figure 1.3). Pushing in on the plunger obviously decreases the volume of the syringes barrel. Because the volume has decreased, the inside surface area has also decreased. This means that the frequency of collisions per unit area has increased, which translates into an increase in pressure. Remember, because pressure is force divided by area, if the area decreases the pressure increases. When we push in on the plunger, the pressure increases to some value above 1 atmosphere. The smaller the syringes barrel volume becomes, the higher the pressure exerted by the air in syringe. The relationship between volume and pressure is known as Boyles Law. Boyles Law was first mentioned in Chapter 3 and is named after Robert Boyle. Simply stated, Boyles

Law says that the pressure and volume of an ideal gas are inversely related, as one goes up, the other goes down. Boyles Law can be stated mathematically as Pressure x Volume = constant Or PV = k So if the gas in the syringe was originally at 1 atmosphere and the volume was 50 mL, then PV would equal 50 atm mL. If we pushed in on the plunger to decrease the volume to 25 mL, then the pressure would have to increase to 2 atmospheres for PV to remain constant. Remember, when we apply Boyles Law, the only two variables that change are pressure and volume. We are assuming the temperature of the gas and the number of molecules of gas in the syringe remain constant. What happens when the pressure of a gas remains constant and the temperature and volume change? Before looking at the relationship between temperature and volume, though, the concept of temperature must be understood. Temperature is one of those terms that is continually used, but rarely given much thought. As long as we can remember, we have had our temperature taken, seen and heard the daily temperature reported, and baked foods at various temperatures. Intuitively, we think of temperature in terms of hot and cold, but what does temperature actually measure? Temperature is a measure of the random motion of the particles making up a substance. Specifically, temperature is a measure of the kinetic energy of the particles in a substance. Kinetic energy is energy of motion. A body possesses kinetic energy when it moves. The formula for kinetic energy is Kinetic Energy = x mass x velocity2 K.E = mv2

Figure 1.3 Pushing in on the plunger decreases the volume, which causes an increase in pressure due to the collision frequency increasing Kinetic energy depends on the mass and velocity of an object. Each of the nitrogen and oxygen molecules in the syringe contain a certain amount of kinetic energy by virtue of the fact that they have mass and are moving. If we could somehow measure the speed of particles in the syringe, we would discover that they move at 5

various velocities. While most move at near some average velocity, some are moving much slower and others much faster than average. A graph of the percent of molecules at a certain velocity versus the velocity is called a Maxwell- Boltzmann distribution, named for Ludwig Boltzmann (18441906) and James Clerk Maxwell (18311879) (Figure 1.4). A velocity of 400 meters per second is roughly 800 miles per hour and represents the typical velocity gas molecules would have at room temperature. The shape of Figure 1.5 is dependent on temperature. At a higher temperature, a greater percentage of the molecules would be moving with greater velocities, and at a lower temperature, a greater percentage with slower velocities (Figure 1.5). Higher and lower velocities translate into higher and lower kinetic energy of the molecules, respectively. We can now consider what a change in temperature means at the molecular level. An increase in temperature implies more energetic particles and a decrease in temperature less energetic particles. When a mercury thermometer is placed in a hot oven, it is exposed to more collisions with greater kinetic energies. The kinetic energy of the gas particles is transferred to the kinetic energy of the mercury, which causes it to expand and register a higher temperature. The expansion of the mercury can be compared to a rack of billiard balls being struck by the cue ball. At the lower temperature, the column of mercury in the thermometer is like the racked balls. An energetic cue ball is like the energetic gas molecules in the oven. The cue ball transfers its kinetic energy to the racked balls causing them to spread out. Similarly, the energetic gas molecules in the oven impart their energy to the mercury atoms causing them to expand up the thermometer column. Cooling would cause the mercurys volume to decrease. If the mercury was cooled to its freezing point of 39C, the formation of solid mercury might be considered analogous to racking up the billiard balls. The two most common scales used to measure temperature are the Fahrenheit and Celsius scales. The German Daniel Fahrenheit (16861736) proposed his temperature scale in 1714 in Holland. Fahrenheit invented the modern mercury thermometer and calibrated his thermometer using three different temperature standards. He assigned a value of 0 to the lowest temperature he could obtain using a mixture of ice, salt, and liquid water. A value of 30 was used for a mixture of ice and freshwater. The third point was set at 96 based on the oral temperature of a healthy person. Using his scale Fahrenheit determined the boiling point of water would be 212. He later changed the standard of the ice-freshwater mixture from 30 to 32 in 6

order to have an even 180 temperature divisions between the freezing and boiling points of water. The latter change resulted in 98.6F being the accepted normal body temperature of a healthy person.

Figure 1.4 Distribution of Speeds in GasMaxwell-Boltzmann Distribution (Rae Djur)

Figure 1.5 Boltzmann Curves at Higher and Lower Temperatures (Rae Djur) Anders Celsius (17011744) from Sweden devised his temperature scale in 1742. Celsius assigned a value of 0 to the boiling point of water and 100 to the temperature of thawing ice. Instrument makers soon reversed the 0 and 100 to give us the modern freezing and boiling points of water as 0C and 100C, respectively. The relationship between the Fahrenheit and Celsius temperature scales are given by the two equations: Degrees Celcius = 5/9 x (Degrees Fahrenheit 32) Degrees Fahrenheit = (9/5 x Degrees Celcius) + 32 Both the Fahrenheit and Celsius temperature scales are based on the physical characteristics of water. The use of water to establish a zero point means that both 0F and 0C are arbitrary and not true zero points. Because temperature is a measure of the random motion of the particles making up a substance, true zero on either the Fahrenheit or Celsius scale would imply that there is no motion at 0F and 0C. We know that substances at these temperatures particles possess an ample amount of motion and kinetic energy. A temperature scale that has a true zero is known as an

absolute temperature scale. One problem that arises when using the Fahrenheit and Celsius temperature scales is because they are not absolute scales, the mathematical comparisons do not make sense. For example, if we compare equal quantities of water at 10C and 20C, we might expect the water at 20C to be twice as hot or have twice as much energy as the water at 10C. This is not the case. As an analogy, consider a child who is 3 feet tall and an adult who is 6 feet tall. Our absolute scale for measuring a persons height is the vertical distance from the bottom of our feet, and using this absolute scale the adult is twice the height of the child. But what if both the child and adult stood on top of 5-foot ladders and we measured their heights from the ground? The child would now measure8 feet and the adult 11. The adult on this revised scale is no longer twice as tall as the child. The Fahrenheit and Celsius temperature scales are like measuring heights of people standing on ladders. It might sound ridiculous to measure people standing on ladders, but the heights would seem normal if thats how we have always measured height. The most common absolute temperature scale used by scientists is the Kelvin temperature scale. The Kelvin temperature scale was proposed by William Thompson, Lord Kelvin (18241907). The Kelvin temperature scale has an absolute zero. True comparisons can be made using the Kelvin scale. A substance at a temperature of 400 Kelvins contains particles with twice as much kinetic energy as a substance at 200 Kelvins. Absolute zero is the temperature where the random motion of particles in a substance stops. It is the absence of temperature. Absolute zero is equivalent to _273.16C. How this value is determined is discussed shortly after we discuss our next gas law. The relationship between Kelvin and Celsius temperature is Kelvins = Degrees Celcius + 273,16 For most work, it is generally sufficient to round off 273.16 to 273. Now that the physical meaning of temperature has been explored, the relationship between temperature and volume of an ideal gas can be examined. Lets consider a syringe containing a specific volume of air at a specific temperature. The syringe is originally at room temperature, about 20C, and placed in a pot of boiling water at 100C. In the boiling water, energy is transferred to the nitrogen and oxygen molecules in the syringe barrel, and they move faster. The number of collisions with the interior walls of the syringes barrel increases. If the pressure within the syringe is to remain constant, the volume must increase. Another way of putting this is that an increase in temperature causes the pressure within the syringe to increase. Because the pressure 8

outside the syringe is 1 atmosphere, the gas will push out on the plunger until the pressure in the syringe returns to 1 atmosphere. There is a direct relationship between temperature and volume of an ideal gas. As temperature increases, volume increases. The direct relationship between temperature and volume in an ideal gas is known as Charleslaw. Jacques Alexandre Charles (17461823) was an avid balloonist. Charles made the first hydrogen-filled balloon flight in 1783 and formulated the law that bears his name in conjunction with his ballooning research. Charles law can be stated mathematically as Volume / Temperatur = Constant V/T = k When applying Charles Law it is important to remember that the absolute temperature must be used. Lets use the syringe example to determine how much the volume would increase if the temperature was raised from20C to 100C. Lets assume the original volume at 20C is 25 mL. First well convert the temperatures to Kelvins, and then apply Charles Law. The calculations are : 200C + 273 = 293 Kelvins 1000C + 273 = 373 Kelvins 25 mL/293 Kelvins = V/373 Kelvins Solving for V, we find that the volume at 100C is approximately 32 mL. Louis Gay-Lussac continued the ballooning exploits initiated by Charles, ascending to over 20,000 feet in a hydrogen balloon in the early 1800s. Gay- Lussacs law defines the relationship between the pressure and temperature of an ideal gas. If the temperature of the air in the syringe increases while keeping the volume constant, the gas particles speed up and make more collisions with the inside walls of the syringe barrel. As we have seen, an increase frequency in the number of collisions of the gas particles with a containers wall translates into an increase in pressure. Gay- Lussacs law says that pressure is directly proportional to temperature. Gay- Lussacs law expressed mathematically is Pressure / Temperatur = Constant P/T = k Again, the temperature must be expressed in Kelvins. If the pressure and temperature of the air in the syringe are originally 1.0 atmosphere and 293 Kelvins and the syringe is placed in boiling water, the pressure will increase to approximately 1.3 atmospheres. The calculations are 9

1,0 atmosphere/293 Kelvins = Pressure Final/373 Kelvins Pressure Final = 1, 0 atmosphere x 373 Kelvins / 293 Kelvins = 1,3 atmosphere The relationship between temperature and pressure provides a method for determining the value for absolute zero. By measuring the pressure of a gas sealed in a constant volume container at different temperatures and extrapolating to a pressure of 0 atmospheres gives the value for absolute zero (Figure 1.6).

Figure 1.6 The value of absolute zero may be determined by extrapolating a plot of pressure versus temperature to a value of 0 atmosphere. This gives a value for absolute zero of _273.16C Boyles, Charles, and Gay- Lussacs laws explain the relationships between pressure, volume, and temperature of an ideal gas. In the examples thus far, the amount of gas in the syringe was considered to be constant. The amount of gas is measured in moles (the standard symbol for moles is n). The Avogadros hypothesis stated that equal volumes of gases contain an equal number of molecules. This means that the volume of a gas is directly proportional to the number of molecules present, and therefore, the number of moles of gas. This relationship is known as Avogadros law. If temperature and pressure are held constant and somehow more molecules are added to the syringe barrel, the volume would increase. A better example to illustrate Avogadros Law is to think about blowing up a balloon. As you blow up the balloon, you are adding more gas molecules (principally carbon dioxide) and the volume increases. It is assumed the pressure and temperature stay constant as the balloon inflates, and that the increase in volume is due to the increase in the number of moles of gas entering the ballon. Because the relationship between pressure and moles is direct, the relationship is expressed mathematically as ; Volume/moles = Constant V/n = k The four fundamental gas laws are summarized in Table 1.3. 10

1.3 The Ideal Gas Law The gas laws discussed in the previous section are limited, because they only allow us to examine the relationship between two variables at a time. Fortunately, all four laws can be combined into one general law called the ideal gas law. The ideal gas law relates the four quantities pressure, volume, moles, and temperature. The ideal gas law is given by the equation Pressure x Volume = Moles x R x Temperature PV = nRT In this equation, R is called the ideal gas law constant. Its value depends on the units used, but assuming pressure is measured in atmospheres, volume in liters, and temperature in Kelvins its value is 0.082 atm-L/mol-K. Table 1.3 Summary of Four Laws for an Ideal Gas

Other forms of the ideal gas law are The four gas laws in the previous section are all special cases of the ideal gas law. We can use the ideal gas law to calculate the volume one mole of gas occupies at standard conditions. Standard conditions are 0C (273 K) and 1 atm pressure. The volume at these conditions is known as a standard molar volume. Plugging the numbers into the ideal gas law equation gives a value of 22.4 liters for the standard molar volume. 1.4 Partial Pressure and Vapor Pressure John Dalton was a contemporary of Charles and Gay-Lussac. As a meteorologist, he had a keen interest in the atmosphere and devoted much of his work to a study of the behavior of gases. Daltons study of gases led him to formulate the law of partial pressure and the concept of vapor pressure. Daltons Law of Partial Pressure states that in a mixture of gases each gas exerts a pressure independent of the pressure exerted by other gases in the mixture. Pi = Xi. Pt ; Xi = mol fraction

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The pressure of the individual gases in the mixture is the partial pressure of that gas. The sum of the partial pressures is the total pressure. Figure 1.7 depicts the concept of partial pressure. Partial pressure is directly related to the moles of gas present. The partial pressures of gases in our atmosphere are approximately0.78 atm for nitrogen, 0.21 atm for oxygen, and 0.01 atm for all the other gases combined. At the same time that Dalton proposed his ideas on partial pressure, he developed the concept of vapor pressure. A vapor is the gaseous form of a substance that normally exists as a solid or liquid. A gas is a substance that exists in the gaseous states under normal conditions of temperature and pressure. The vapor pressure of a liquid is the partial pressure of the liquids vapor at equilibrium. Liquids with strong intermolecular forces exert lower vapor pressures than those with weak intermolecular forces. In liquids with strong intermolecular forces, it is more difficult for the molecules to leave the liquid state and enter the gaseous state.

Figure 1.7 Daltons Laws of Partial Pressure states that in a mixture of gases each gas exerts a pressure independent of the other gases. The total pressure is the sum of the partial pressures Liquids with high vapor pressures are known as volatile liquids. To understand vapor pressure, lets consider an empty jar that is partially filled with water and then covered with a lid. We will assume the space above the water in the jar contains only air when we screw on the jars lid. After the lid is place on the jar, water molecules leave the liquid and enter the air above the liquids surface. This process is known as vaporization. As time goes by, more water molecules fill the air space above the liquid, but at the same time, some gaseous water molecules condense back into the liquid state. Eventually, a point is reached where the amount of water vapor above the liquid remains constant. At this point, the rates of vaporization and condensation are equal, and equilibrium is reached. The partial pressure exerted by the water at this point is known as the equilibrium vapor pressure or just vapor pressure. Vapor pressure is directly related to the temperature, that is, the higher the temperature, the higher the vapor pressure. Table 1.4 gives the vapor pressure of water at several temperatures. The amount of

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water vapor in the air is known as humidity. Relative humidity is the ratio of the actual vapor pressure compared to the equilibrium vapor pressure at a particular temperature. If the vapor pressure was 14.0 at a temperature of 20C, then the relative humidity would be 14.0/17.5 _ 80%. The vapor pressure of a liquid dictates when a substance will boil. In fact, the boiling point of a substance is defined as the temperature at which the vapor pressure equals the external pressure. Typically, the external pressure is equal to atmospheric pressure, and we define the normal boiling point as the temperature when the vapor pressure equals 1 atmosphere. If we consider water heated on a stove, the bubbles that develop in the liquid contain water vapor that exerts a pressure at the specific vapor pressure of water at that temperature. For example, when water reaches 60C, any bubbles that form will contain vapor at 149 mm Hg (see Table 1.4). Table 1.4 Vapor Pressure of Water at Different Temperatures

At this pressure, and any other pressure below 760 mm Hg (1 atmosphere), the external pressure of 1 atmosphere causes the bubbles to immediately collapse. As the temperature of the water rises, the vapor pressure continually increases. At 100C, the vapor pressure inside the bubbles finally reaches 760 mm Hg. The vapor pressure is now sufficient to allow the bubbles to rise to the surface without collapsing. At higher elevations where the external pressure is lower, liquids boil at a lower temperature. At the top of a 15,000-foot peak, water boils at approximately 85C rather than 100C. This increases the cooking time for items, as noted in the directions of many packaged food. If the external pressure is increased, the boiling temperature also increases. This is the concept behind a pressure cooker. The sealed cooker allows pressure to build up

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inside it and increases the boiling point allowing a substantial increase in cooking temperature and decrease in cooking time. 1.5 Applications of the Gas Laws The pressure cooker is just one practical example of the behavior of gases in everyday life. In this section, we look at a few more relevant examples involving gases. A process analogous to the pressure cooker which we all can relate to is popping corn. Each kernel of corn contains about 15% water. The hard kernel acts as a constant volume container. When the kernel is heated, the temperature increases, and according to Gay- Lussacs law, the pressure increases. A small amount of the water inside the kernel vaporizes into superheated steam, but most of the water remains in liquid form because of the increased pressure. At some point when the pressure increases to several atmospheres, the kernel pops as the steam transforms the starchy kernel into gelatinous globules of popped corn. One national news story in the year 2000 involved the defect in certain brands of tires and how tread separation caused vehicle accidents leading to personal injury and in some cases deaths. One prominent aspect of the tire story involved whether the tires were properly inflated to the correct pressure. The air inside a tire can be considered an ideal gas, and we can apply the gas laws to the air inside. The inflation pressure recommendations stamped on the sides of tires call for tires to be inflated under cold conditions, or before the vehicle is driven. Because the most important aspect of tire performance is correct inflation pressure, it is important to adhere to the recommended tire pressure. Many individuals disregard this recommendation. It is not uncommon for someone to pull into a gas station and fill a warm tire to the recommended pressure. How much can this affect the pressure in the tire? In this example, the important variables are pressure and temperature. We will assume that the amount of air in the tire and volume of the tire are constant, and will see how much of an error can be introduced by ignoring the inflation temperature. Lets assume the recommended inflation pressure is 30 pounds per square inch (psi), and we fill the tire on a hot day after pulling off the freeway and the tire temperature is 90F (32C). We will assume the cold pressure applies to a temperature of 70F (21C). Gay-Lussacs law can be applied to determine the actual cold inflation pressure. We can write GayLussacs Law as 14

Pcold/Tcold = Phot/Thot

Pcold = 30 psi x 294 K/ 305 K = 28,9 psi

This is a relatively small change, but consider the change if you inflate the tire in a heated garage at 70F and then drive in winter when the temperature is 10F. In this case, the pressure drop would be approximately5 psi. A pressure change of this much can lead to as much as a 25% reduction in fuel efficiency. Additionally, under inflated tires result in overloading and possible tire failure. Reduced tire pressures of as little as 4 psi were cited in some of the national stories involving tire failure and vehicle accidents. Another area in which the gas laws play a key role is in scuba diving. At the surface, we breath air at a pressure of approximately 1 atmosphere. The partial pressures of nitrogen and oxygen are 0.78 and 0.20 atmosphere, respectively. A scuba diver breaths compressed air that is delivered at a pressure that corresponds to the pressure at the depth of the diver. Because 33 feet of water corresponds to 1 atmosphere of pressure, a diver at 33 feet would breath air at a total pressure of 2 atmospheres; one atmosphere of this pressure is due to the air pressure at sea level and 1 atmosphere is due to the pressure of the water. The partial pressures of the nitrogen and oxygen would be twice as great as that at the surface. Most serious problems in diving arise when divers descend to depths in excess of 100 feet. The total pressure at depths greater than 100 feet can cause problems such as nitrogen narcosis and oxygen toxicity. Nitrogen narcosis, also known as rapture of the deep, is due to breathing nitrogen under pressure. At a depth of 100 feet, the total pressure of air delivered to the diver is about 4 atmospheres. This results from a water pressure of slightly greater than 3 atmospheres plus the surface air pressure of 1 atmosphere. The partial pressure of nitrogen at this depth would be about 3.2 atmospheres. Nitrogen at this pressure produces an anesthetizing effect similar to nitrous oxide (laughing gas). The result is a state of nitrogen intoxication with loss of judgment, a state of euphoria, drowsiness, and impaired judgment. If nitrogen narcosis develops, it can be quickly reversed by moving to a shallower depth. To prevent nitrogen narcosis, deep divers use a mixture of helium, oxygen, and nitrogen. Helium is much less soluble in body tissues and like nitrogen is inert and does not play a role in metabolism. Another example of a diving problem that is a direct consequence of Daltons Law of partial pressure concerns oxygen toxicity. The deeper a diver descends, the greater the partial pressure of oxygen. At a depth of 130 feet, the total pressure is close to 5 atmospheres and the partial pressure of oxygen will be close to 1 15

atmosphere (21% _ 5 atmospheres). What this means is that breathing compressed air at 130 feet is like breathing pure oxygen at the surface. Breathing pure oxygen or breathing compressed air at 130 feet is only a problem if done for several hours. Oxygen toxicity can damage the lungs, affect the nervous system, and in extreme cases, result in seizures. Recreational divers do not stay down long enough at great depths for this to become a problem, but it can be a problem for commercial divers. When the partial pressure of oxygen approaches 2 atmospheres, it may take only several minutes for symptoms of oxygen toxicity to appear. To prevent oxygen toxicity, divers use a lower percentage of oxygen for deep dives. For example, a diver at 200 feet might breath from a tank that contains only 4% oxygen. Both nitrogen narcosis and oxygen toxicity involve deep diving. Other problems result when the diver ascends too quickly. We know from Boyles Law that as pressure decreases, volume increases. Decompression sickness develops when a diver ascends too fast and nitrogen bubbles develop in the tissue. Symptoms may include dizziness, paralysis, shock, and joint and limb pain. The term the bends comes from the pain that appears in body joints such as the elbows, knees, ankles, and shoulders. During a normal ascent from moderately deep depths (greater than 60 feet), a diver must be sure to take scheduled stops and allow gases such as nitrogen to come out of the body tissue slowly. Another serious problem with surfacing too quickly is an air embolism. An air embolism develops when air expands in the lungs and bubbles are forced into the blood vessels, possibly cutting off blood flow to the brain and resulting in a loss of consciousness. Both decompression sickness and air embolism can be treated by placing the victim in a hyperbaric chamber. Hyper means greater or above normal and baric means weight or pressure. In a hyperbaric chamber, the victim is placed in an environment of increased pressure and enriched oxygen. By decreasing the pressure slowly, the gases can come out slowly. The enriched oxygen in the hyperbaric chamber helps to purge and dilute the nitrogen in the tissues. A final example of a practical application of the ideal gas law involves snow making. Many ski resorts and Hollywood often employ snow guns to produce their own snow (Figure 1.8). A snow gun essentially uses compressed air to atomize water into droplets. The droplets are sprayed into the air where they condense into ice crystals. As the compressed air and water droplets leave the snow gun, the decrease in pressure causes the air to expand resulting in a drop in 16

temperature. The cooling of air as it expands is also demonstrated when moist air masses from the Pacific move inland over the West Coast. The air masses will ride up the western edge of coastal mountain ranges such as the Cascades. As this moistureladen air moves to higher elevations, the pressure decreases causing the air to expand and cool. When the relative humidity reaches 100%, precipitation results in the form of rain or snow. On the eastern side of the mountains, dry air masses descend and become compressed as they are subjected to increased pressure at lower elevations. This results in dry, desert like conditions on the eastern side of the coastal mountain ranges. The few examples illustrated above demonstrate how gases and the gas laws affect our lives on a daily basis. We are surrounded by gas and our lives are dependent on a steady supply of gas. Humans can survive a few weeks without food, a few day swith out water, but only a few minutes without a steady supply of air. In this chapter, we have focused on some of the unique properties of gases and the gas laws.

Figure 1.8 Snow Gun Summary : 1. Pressure is defined as the force exerted per unit area. 2. Kinetic energy depends on the mass and velocity of an object. 3. The pressure of the individual gases in the mixture is the partial pressure of that gas. The sum of the partial pressures is the total pressure. Problems ; 1. Calculate the density of air at 0 C and 1 atm, if the composition at mass percent is N2 = 74,7%, O2 = 22,9%, Ar = 1,3 % H2O = 1%, CO2 = 0,1 %. 2. The mixture of N2 and O2 gas have density 1,185 g/L at 25 C and 1 atm. Calculate the mol fraction and partial pressure of N2 and O2. 17