Gases

Youll Need to Know

the properties of gases how to work with mole fractions how to calculate either pressure or temperatures given data and change from Celsius to Kelvin how to solve problems involving the following gas laws: Avogadros Law Boyles Law Charles Law Combined Gas Law Daltons Law of Partial Pressure gas density Gay-Lussacs Law Grahams Law of Diffusion-Effusion Ideal Gas Law van der Waals Equation the concepts of kinetic molecular theory how to answer questions that involve the Maxwell-Boltzmann Distribution

Properties of Gases
The following are some properties of gases:

All elements in Group 8A are gases (noble gases). Elements that are gases at room temperature and pressure are nonmetals. Gases assume the volume and shape of their container. Gases have significantly lower densities and are more easily compressed than liquids or solids. Gases mix evenly and completely when confined to the same container.

Mole Fractions
A mole fraction is a dimensionless quantity that expresses the ratio of the number of moles of one component to the number of moles of all other components present. The symbol for the mole fraction of gas A is XA, total pressure of all gases is PT and the pressure of gas A is PA. P X A = PA or PA = X A $ PT T

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Example
Q. A mixture of gases contains 1.00 mole of neon, 2.00 moles of argon, and 3.00 moles of xenon. The total pressure of the gas mixture is 2.00 atm. What is the partial pressure of the argon gas? A. 0 atm B. 0.333 atm C. 0.667 atm D. 1.50 atm E. 3.33 atm 2.00 mol n A. C. X Ar = n + n Ar + n = = 0.333 1.00 mol + 2.00 mol + 3.00 mol Ne Ar Xe PAr = XAr PT = 0.333 2.00 atm = 0.667 atm

Pressure and Temperature

Normal atmospheric conditions are 25C (298K) and 1 atm pressure. 760 mm Hg = 1 atm = 101.325 kPa, 1 torr = 1 mm Hg Gases that are collected after they have bubbled through water also contain water vapor molecules (i.e., the gas is wet). These water molecules must be gotten rid of as they increase the pressure of the system. Always subtract the water vapor pressure (given at various temperatures) from the total pressure of the gas to get just the pressure of the dry gas. When solving gas problems, always convert Celsius to Kelvin: C + 273 = K

STP
Standard temperature is 0C (273K) and standard pressure = 1 atm. Under these conditions, 1 mole of any gas (6.02 1023 particles) occupies 22.4 liters.

Gas Laws
The volume of a gas is directly proportional to the number of moles of the gas present (pressure and temperature held constant). V"n Avogadros Law V1n2 = V2 n1 Volume Avogadros Law

Amount (moles)

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Volume is inversely proportional to pressure (temperature held constant). V" 1 P

Boyles Law P1V1 = P2V2 Volume V

Pressure P Volume is proportional to the absolute temperature of a gas (pressure held constant). V"T

V1T2 = V2T1

Volume V

Charles Law

Temperature T (K) Combined Gas Law P1V1 P2 V 2 = T1 T2 A combination of Boyles, Charles, and Gay-Lussacs laws interrelating temperature, volume, and pressure. The total pressure of a mixture of gases is the sum of the individual pressures. The partial pressure of any gas (Pi ) in the system is equal to the mole fraction of that gas (Xi ) times the total pressure of the system (PT).

Daltons Law of Partial Pressure PT = P1 + P2 + P3 + . . . Pi = Xi PT

Gas Density d= m = P$M V R$T

(continued)

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At constant volume, the pressure exerted by a given mass of gas varies directly with the absolute temperature. P"T Gay-Lussacs Law Gay-Lussacs Law Pressure Absolute Temperature The rates of diffusion (or effusion) for gases are inversely proportional to the square roots of their molecular masses. Diffusion is the gradual mixing of molecules of one gas with molecules of another. Effusion is the process by which a gas under pressure escapes from a small opening. The equation of state of an ideal gas, which is a good approximation to real gases at sufficiently high temperatures and low pressures. The behavior of real gases usually agrees with the predictions of the ideal gas equation to within 5% at normal temperatures and pressures. At low temperatures or high pressures, real gases deviate significantly from ideal gas behavior. P1T2 = P2T1

Grahams Law of Diffusion-Effusion r1 r2 = M2 M1

Ideal Gas Law PV = nRT

van der Waals Equation

dP +

n 2 a V - nb = nRT n^ h V2

Examples
Q. A balloon with 3 moles of gas particles has an initial volume of 7.0 L. If 6.0 additional moles of gas particles are introduced into the balloon, under conditions of constant P and T, what will the new volume of the balloon be? 9 moles n = 21L A. V 2 = V1 # n 2 = 7.0 L # 1 3 moles Q. A balloon has a volume of 4.0 L at sea level on a day where the atmospheric pressure was measured at 1.0 atm. The balloon is let go and rises to a height of 4 miles where the pressure is about 0.40 atmospheres. What is the final volume of the balloon at this height (assume the temperature did not change)? 1.0 atm P A. V 2 = V1 # P1 = 4.0 L # 0.40 atm = 10. L 2 Q. A 300. mL sample of oxygen gas is heated from 27C to 77C at constant pressure. What is the final volume? A. Begin by changing temperatures to K: T1 = 27C + 273 = 300K T2 = 77C + 273 = 350K 350 K T V 2 = V1 # T 2 = 300. mL # 300 K = 350. mL 1

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Q. A gas-filled balloon having a volume of 5.00 L at 3.00 atm and 27C is set free and rises to an altitude where the temperature is 73C and the pressure is 1.00 atm. Calculate the final volume of the balloon. A. P1 = 3.00 atm P2 = 1.00 atm V1 = 5.00 L V2 = ? T1 = 27C + 273 = 300K T2 = 73C + 273 = 200K

_ 3.00 atm i_ 200 K i P T V 2 = V1 P1 # T 2 = 5.00 L # = 10.0 L 2 1 _1.00 atm i_ 3500 K i

Q. A mixture of gases contains 4.00 moles of neon, 1.00 mole of argon, and 3.00 moles of xenon. Calculate the partial pressures of the gases if the total pressure is 6.00 atm at a certain temperature. 4.00 moles n = 0.500 A. mole fraction of neon X Ne = n + n Ne + n = 4.00 mol + 1.00 mol + 3.00 mol Ne Ar Xe PNe = XNe PT = 0.500 6.00 atm = 3.00 atm 1.00 moles n mole fraction of argon X Ar = n + n Ar + n = = 0.125 4.00 mol + 1.00 mol + 3.00 mol Ne Ar Xe PAr = XAr PT = 0.125 6.00 atm = 0.750 atm 3.00 moles n mole fraction of xenon X Xe = n + n Xe + n = = 0.375 4.00 mol + 1.00 mol + 3.00 mole Ne Ar Xe PXe = XXe PT = 0.375 6.00 atm = 2.25 atm Q. Calculate the density (in grams per liter) of a gas whose molar mass is 100. g mol1 at 380. mm Hg and 27C. A. T = 27C + 273 = 300 K MM = 100. g mol1 P = 380 mm Hg / 760 mm Hg = 0.50 atm m $ d = V = PR MM = $T

_ 0.50 atm ia 100. g $ mol - 1 k

1

_ 0.0821L $ atm $ mol

-1

$K

-1

i d 300 K n
3

. 2.0 g $ L- 1

Q. The temperature of a gas sample is increased from 50.C to 100.C. By what factor must the pressure be changed if the volume is to be kept constant? A. 0.5 B. 0.75 C. 1.15 D. 2.0 E. 4.0 A. C. Let P1 = 1.00 atm T1 = 50.C + 273 = 323 K T2 = (100.C + 273) = 373 K
^1.00 atmh_ 373 K i P1 T P2 = T 2 = = 1.15 atm 323 K 1

Q. Gas A has a molar mass of 27.00 g mol1 while gas B has a molar mass of 3.00 g mol1. How much faster or slower will gas B effuse from a small opening compared to gas A at the same temperature? rB A. r A = 27.00 g $ mol - 1 MA = = 9.00 = 3.00 MB 3.00 g $ mol - 1

Gas B will effuse 3 times faster than gas A.

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Q. Calculate the volume (in liters) occupied by 88.02 grams of carbon dioxide gas at 27C and 2.0 atm. 88.02 g CO 2 = 2.000 mol P = 2.0 atm T = 27cC + 273 = 300 K A. n = 44.01 g $ mol - 1 _ 2.000 mol i_ 0.0821L $ atm i_ 300 K i V = nRT = . 25 L P _ mol $ K i_ 2.0 atm i Q. 2.50 moles of carbon dioxide gas at 500K has a volume of 5.00 L. The van der Waals correctional value for the attractiveness of gas molecules, (a) = 3.6 atm L2 mol2 and the van der Waals correctional value for molecular size (b) = 0.05 L/mol. Without doing calculations, show how the problem would be set-up to solve for pressure. A. n = 2.50 moles V = 5.00 L T = 500K a = 3.6 atm L2 mol2 b = 0.05 L/mol P= nRT - an 2 V - nb h V 2 ^
2 2

2 _ 2.50 molesi_ 0.0821 L $ atm $ mol - 1 $ K - 1 i_ 500. K i a 3.6 atm $ L /mol k_ 2.50 mol i 2 5.00 L - _ 2.50 moles $ 0.05 L/mol i _ 5.00 L i

Kinetic Molecular Theory

The kinetic-molecular theory has five basic assumptions:

Gases consist of large numbers of molecules (or atoms, in the case of the noble gases) that are in continuous, random motion. The volume of all the molecules of the gas is negligible compared to the total volume in which the gas is contained. Attractive and repulsive forces between gas molecules are negligible. The average kinetic energy of the molecules (K.E. = 12 mv2 ) does not change with time (as long as the temperature of the gas remains constant). Energy can be transferred between molecules during collisions (but the collisions are perfectly elastic). The average kinetic energy of the molecules is proportional to absolute temperature. At any given temperature, the molecules of all gases have the same average kinetic energy. In other words, if you have two gas samples, both at the same temperature, then the average kinetic energy for the collection of gas molecules in one sample is equal to the average kinetic energy for the collection of gas molecules in the other sample.

The Maxwell-Boltzmann Distribution

In any mixture of gas particles, the molecular speeds will vary a great deal, from very slow particles (low energy) to very fast particles (high energy). Most of the particles however will be moving at a speed very close to the average. The Maxwell-Boltzmann distribution shows how the speeds (and hence the energies) of a mixture of moving particles varies at a particular temperature. Points to remember include:

the area under the curve equals the total molecules in the sample and doesnt change there are no molecules with zero energy very few molecules have high energies there is no maximum energy for a molecule

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the most probable energy value is where the curve is at its highest if you increase the temperature of the sample, the distribution changes as shown in the diagram below. The curve becomes stretched out and has a lower peak, but the area under the curve remains the same

Number of molecules

where rms is known as the root mean square and is a measure of the velocity of particles in a gas and is defined as the square root of the average velocity-squared of the molecules in a gas. m = mass, M = molar mass KE per molecule = 12 m2 KE per mole = (32)RT 1 J = 1 kg m2 s2 R = 8.314 J K1 mol1

rs

am

kT RT y rms = 3m = 3M
co l de

pl wa rm er sa m pl e

Energy

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