Class : IX

CHEMISTRY - GASEOUS STATE

STUDY MATERIAL

Gases The first step to understanding gases is to spell out what exactly a gas is. Gases have two properties that set them apart from solids and liquids. First, gases spontaneously expand to fill the container they occupy, no matter its size. In other words, a gas has no fixed volume or shape. Secondly, gases are easily compressible. You can imagine a gas as a busy swarm of molecules. Each molecule moves randomly and travels great distances before bouncing off another molecule. This occurs because the individual molecules comprising a gas are generally far apart. In fact, for a gas at low pressure, we can approximate that aside from a few random collisions, individual gas molecules do not interact. This approximation is what separates gases from solids and liquids, whose molecules always interact. The ideal gas law macroscopically describes how gases behave under nearly all conditions. The kinetic molecular theory describes how sub-microscopic gas molecules interact with each other. Pressure Of the three general terms used to describe gases (volume, temperature, pressure), pressure is the least familiar. Before we can delve into the gas theories, we need a firm understanding of it. Pressure is defined as force divided by the area over which the force acts: P=F/A Ice skates are familiar examples of the effects of pressure. The area of the blades of a skate are much smaller than, say, the soles of your feet. So if you strap on ice skates, your weight will act on an area much smaller than it would if you were wearing normal shoes. Since A decreases while F stays the same, by @@Equation@@, the pressure you exert on the ice will be much greater if you're wearing skates. This pressure is often enough to melt a layer of ice, which allows your skate to glide smoothly across an ice rink. If you try the same maneuver with normal shoes, you will not generate enough pressure to melt the ice and won't get anywhere fast. So how does pressure relate to gases? If you will remember, a gas will fill any container that holds it. It is easy to see why with our swarm analogy. If a compact swarm of molecules is placed into a large container, the individual molecules will move about randomly and eventually stray from their original dimensions. Eventually, some intrepid molecules will reach the walls of the container. When they do, they will impact the walls of the container. These impacts generate a force, and hence a pressure on the walls of the container.

Atmosphere - A unit of measurement defined as 101,325 Pascals. The typical pressure at sea level varies around one standard atmosphere (atm). Atmospheric pressure P can be calculated via the following equation: P = hg Bar - A unit of measurement equivalent to 1105 Pascals. Barometer - A device used to measure atmospheric pressure.

Barometers. mm Hg - A unit of pressure commonly used with the barometer. It corresponds to 1 torr and 1/760 atm at 0 o Celsius only. Pascal - The SI unit of pressure. 1 Pascal = 1 N/m2 . Pounds per Square Inch - A unit of pressure commonly used in the United States. 1 psi = 1 lb in-2 . 14.6960 psi corresponds to one atmosphere. Pressure - Pressure = Force/Area. The standard atmospheric pressure is 101,325 Pascals. Torr - A unit of pressure closely related to mm Hg, but more convenient and absolute. 1 Torr = 1 mm Hg at 0 o Celsius. 1 Torr always equals 1/760 atm, irrespective of the temperature. Boyle's Law and the Manometer Boyle's Law The most important thing to remember about Boyle's Law is that it only holds when the temperature and amount of gas are constant. A state of constant temperature is often referred to as isothermal conditions. When these two conditions are met, Boyle's law states that the volume V of a gas varies inversely with its pressure P . The equation below expresses Boyle's law mathematically: PV = C. C is a constant unique to the temperature and mass of gas involved. plots pressure versus volume for a gas that obeys Boyles law.

Figure :Pressure versus Volume You will get the most mileage out of another incarnation of Boyle's law: P1V1 = P2V2

The subscripts 1 and 2 refer to two different sets of conditions. It is easiest to think of the above equation as a "before and after" equation. Initially the gas has volume and pressure V 1 and P 1 . After some event, the gas has volume and pressure V 2 and P 2 . Often you will be given three of these variables and asked to find the fourth. You should realize that this is a simple case of algebra. Separate the knowns and unknowns on two different sides of the "=" sign, plug in the known values, and solve for the unknown. The Manometer Boyle used a manometer to discover his gas law. His manometer had an odd "J" shape:

Figure :A Manometer As you can see from , there are two ends to Boyle's manometer. One end is open to the atmosphere. The other end is sealed, but contains gas at atmospheric pressure. Since the pressure on both ends of the tube is the same, the level of mercury is also the same. Next Boyle added mercury to the open end of his manometer.

The volume of the gas at the closed end of the manometer decreased, but since gas can't get in or out of the closed end, the amount of gas does not change. Likewise we can assume that the

experiment occurs under isothermal conditions. Boyle's law should hold, meaning that the initial volume times pressure should equal the volume times pressure after the additional mercury was added. Let's use the equation below on the gas at the sealed end: P1V1 = P2V2 The pressure of the gas before mercury is added is equal to the atmospheric pressure, 760 mm Hg (let's assume that the experiment is run at o C so that 1 torr = 1 mm Hg). So P 1 = 760 mm Hg. The volume V 1 is measured to be 100 mL. After Boyle added mercury, the volume of the gas, V 2 , drops to 50 mL. To find the value of P P2 = P1 V1 / 2 = (100 mL)(760 mm Hg)/(50 mL) 2 , rearrange the equation above and plug in values: = 1520 mm Hg If you look back at , you'll notice that the difference P 2 - P 1 = 760 mm Hg, and that this exactly equals the difference in mercury levels on the two sides, h . In fact, Boyle's manometer illustrates a truism common to all manometers: h corresponds to the difference in pressure between the two ends of the manometer. Boyle's manometer is only one of the many kinds of manometers you'll face. Don't be disheartened; all manometers are practically the same. Realize that each end of a manometer can only be:

sealed and contain a vacuum ( P = 0 ) open to the atmosphere ( P = P atm ) open to a sample of gas with pressure P

This is the key to solving manometer problems. Once you figure out the pressure at both ends of the manometer, you can use the difference to determine the height h of the liquid column, and vice versa. Let's try this procedure with a manometer in which one end is open to the atmosphere (760 mm Hg) and the other is sealed off to a vacuum.

At the end that is sealed off with a vacuum, P = 0 mm Hg. At the end open to the atmosphere, P = 760 mm Hg. The difference between the two pressures is 760 mm Hg, so the height h must correspond to 760 mm Hg, the atmospheric pressure. Thus this manometer has the same function as a barometer; it measures atmospheric pressure.

There are a few other flavors of manometer, but you can handle them if you remember that h is the pressure difference between the two sides of the manometer. Note that the side of the manometer with the highest pressure also has the lowest level of Hg. Problem : Graph the pressure vs. volume relationship dictated by Boyle's law. If Boyle's law stated that P = aV , where a < 0 , what would the graph of P vs. V look like? A graph of P vs. V according to Boyle's law is shown below:

Fig (1) Boyle's Law When P = aV , the graph of P vs. V will look like this:

fig(2)

P = aV Note that P = aV cannot be true. The equation predicts negative volumes as P increases. (fig 2) Problem : One end of a mercury filled manometer is open to the atmosphere, while the other is closed and contains a vacuum. What does the height difference h of the Hg columns measure?

h measures the difference in pressure between the two ends of the manometer. Since the pressures at the two ends are 0 and P atm , the height h will measure the atmospheric pressure. Problem : The pressure of gas A ( P A ) is 3.0 atm. The height of the mercury column h is 1140 mm. What is the pressure of gas B ( P B ) in atmospheres? Assume that 1 mm Hg = 1/760 atm.

From the diagram we can see that P A must be greater than P B by 1140 mm of Hg. 1140 mm Hg converts to 1.5 atm, so P B = 3.0 - 1.5 = 1.5 atm. Charles, Avogadro, and the Ideal Gas Law Charles' Law Charles' law states that, at a constant pressure, the volume of a mixed amount of gas is directly proportional to its absolute temperature: =k Where k is a constant unique to the amount of gas and pressure. Just as with Boyle's law, Charles' law can be expressed in its more useful form: =

The subscripts 1 and 2 refer to two different sets of conditions, just as with Boyle's law. Why must the temperature be absolute? If temperature is measured on a Celsius (non absolute) scale, T can be negative. If we plug negative values of T into the equation, we get back negative volumes, which cannot exist. In order to ensure that only values of V 0 occur, we have to use an absolute temperature scale where T 0 . The standard absolute scale is the Kelvin (K) scale. The temperature in Kelvin can be calculated via T k = T C + 273.15 . A plot of the temperature in Kelvin vs. volume gives :

Figure :Temperature vs. Volume

As you can see from , Charles' law predicts that volume will be zero at 0 K. 0 K is the absolutely lowest temperature possible, and is called absolute zero. Avogadro's Law Avogadro's law states that the volume of a gas at constant temperature and pressure is directly proportional to the number of moles of gas present. It's mathematical representation follows: fracVn = k k is a constant unique to the conditions of P and T . n is the number of moles of gas present. 1 mole (mol) of gas is defined as the amount of gas containing Avogadro's number of molecules. Avogadro's number ( N A ) is N A = 6.0221023 1 mol of any gas at 273 K (0_C) and 1 atm has a volume of 22.4 L. The conditions 273 K and 1 atm are the standard temperature and pressure (STP). STP should not be confused with the less common standard atmospheric temperature and pressure (SATP), which corresponds to a temperature of 298 K and a pressure of 1 bar. The numbers 22.4 L, 6.0221023 , and the conditions of STP should be near and dear to your heart. Memorize them if you haven't already. The Ideal Gas Law Charles', Avogadro's, and Boyle's laws are all special cases of the ideal gas law: PV = nRT T must always be in Kelvin. n is almost always in moles. R is the gas constant. The value of R depends on the units of P , V and n . Be sure to ask your instructor which values you should memorize. Units Value of R

0.08206

8.314

8.314

1.987

62.36

You can think of R as a converter that changes the units on the right side of the above equation to the units on the left side of the "=" sign. The values 0.0821 most use. Memorizing them will make your life easier. and 8.314 get the

The ideal gas law is the equation you must memorize for gases. It not only allows you to relate P , V , n and T , but can replace any of the three classical gas laws in a pinch. For example, let's say you're given constant values of P and n , but forget how Charles' law relates V and T . Rearrange the ideal gas law to separate the constants and unknowns: = =k

Voila! We have derived Charles' law from the ideal gas law. n , R , and T are constants, so the constant k from Charles' law. The ideal gas law is also useful for those rare occasion when you forget the value of a

is just

constant. Let's say I forgot the value of R in . If I remember that a mole of gas has a volume of 22.4 L at STP (760 torr, 273 K), I can rearrange PV = nRT to solve for R in the desired units. It is much more efficient to memorize the values, but it is comforting to know that you can always fall back on good old PV = nRT . Applying the Ideal Gas Law Ideal gas law problems tend to introduce a lot of different variables and numbers. The sheer amount of information can be confusing, and it is wise to develop a systematic method to solve them: 1) Jot down the values of P , V , n , and T . If the question says that one of these variables is constant or asks you to find the value of one or the other, make a note of it. Every time you encounter a numerical value or variable, try to fit it into your PV = nRT scheme. 2) Rearrange PV = nRT such that the unknowns and knowns are on opposite sides of the "=" sign. Make sure that you are comfortable with the algebra involved. 3) Convert to the appropriate units. Generally you'll want to deal with SI units ( m 3 , Pa, K, mol). There will be times that non-SI units will be more convenient. In these cases, remember that T must always be in Kelvin. Make sure to select the correct value and units of R . 4) Plug in values and solve for the unknown(s). Ideal gas problems involve a great deal of algebra. The only way to master this type of problem is to practice. Use the problems provided at the end of this section and your textbook until the manipulations of PV = nRT become familiar. 5) Take a step back and check your work. The easiest way to do this is to carry all of the units through your ideal gas calculations. When you're about to solve the equation, make sure that the units on both sides of the "=" sign are equivalent. For simpler problems, it is also worthwhile to make sure that your answer makes sense. For example, if n , R , and T are constant and P rises, make sure that V decreases. It only takes a few seconds, and can save you from some embarrassing mistakes. The usefulness of such commonsense checks decreases as the questions get more complex. For any

problem where more than two variables change, you're better off trusting the ideal gas law and your own algebra. The best advice I can give you is to practice. The more problems you do, the more comfortable you will be with the ideal gas law.