Gases

Chapter 5

General properties of gases

There is a lot of free space in a gas. Gases can be expanded infinitely. Gases fill containers uniformly and completely. Gases diffuse and mix rapidly. Gas properties can be modeled using math. Model depends on: V = volume of the gas (L) T = temperature (K) ALL temperatures in the entire chapter MUST be in Kelvin!!! No Exceptions! n = amount (moles) P = pressure (atmospheres)

5.1. Pressure
Pressure of air is measured with a BAROMETER Hg rises in tube until force of Hg (down) balances the force of atmosphere (pushing up). Pressure of Hg pushing down related to Hg density column height Column height measures Pressure of atmosphere 1 standard atmosphere (atm) = 760 mm Hg (or torr) = 14.7 pounds/in2 (psi) = 101.3 kPa (SI unit is PASCAL) = about 34 feet of water!

Pressure Conversions
A. What is 475 mm Hg expressed in atm? 1 atm 760 mm Hg = 0.625 atm

475 mm Hg x

B. The pressure of a tire is measured as 29.4 psi. What is this pressure in mm Hg? 760 mm Hg = 1.52 x 103 mm Hg 29.4 psi x 14.7 psi

Pressure Conversions
A. What is 2 atm expressed in torr?

B. The pressure of a tire is measured as 32.0 psi. What is this pressure in kPa?

5.2. The Gas Laws of Boyle, Charles, and Avogadro

Boyles Law
P1V1 = P2 V2 or PV= k This means Pressure and Volume are INVERSELY PROPORTIONAL if moles and temperature are constant. For example, P goes up as V goes down.

V 1/P

Robert Boyle (1627-1691)

A bicycle pump is a good example of Boyles law. As the volume of the air trapped in the pump is reduced, its pressure goes up, and air is forced into the tire.

V= k

1 P

y=mx+ b (x = 1/P, b= 0, m=k)

Limitations of Boyles law: The law hold precisely at low pressures (<1 atm) At high pressures, the dependence of PV on pressure becomes obvious A gas that strictly obeys Boyles law is called an ideal gas

Charless Law

If moles and pressure are constant, then V and T are directly proportional V= bT V1 T1
=

V2 T2 Jacques Charles (17461823). Isolated boron and studied gases.

If the temperature goes up, the volume goes up!

Charles made the first balloon flight

Charless original balloon

Modern long-distance balloon

Plots of V versus T V= bT The volume of each gas is directly proportional to temperature and extrapolates to zero when the temperature is 0 K. 0 K is absolute zero, cannot be reached. In laboratories temperature as low as 0.000001 K is produced.

Avogadros law
Equal volumes of gases at the same temperature and pressure contain the same number of particles. (molecules) V= a.n n is number of moles of gas, a is a proportional constant For a gas at constant temperature and pressure, the volume is directly proportional to the number of moles of gas.

5.3. The ideal gas law

Boyles law V=k/P (at constant T and n) Charless law V= bT (at constant P and n) Avogadros law V= an (at constant T and P)

Combining these laws gives the ideal gas law: PV=nRT R is universal gas constant, has the value 0.08206 L.atm/K.mol A particular state of a gas is defined by its pressure, volume, temperature and number of moles. The ideal gas law is called the equation of state. The ideal gas law is a limiting law which applies well at low pressures and high temperatures

Deviations from Ideal Gas Law

Real molecules have volume. The ideal gas consumes the entire amount of available volume. It does not account for the volume of the molecules themselves. There are intermolecular forces. An ideal gas assumes there are no attractions between molecules. Attractions slow down the molecules and reduce the amount of collisions. Otherwise a gas could not condense to become a liquid.

Practice problem
How much N2 is required to fill a small room with a volume of 960 cubic feet (27,000 L) to 745 mm Hg at 25oC?
Solution

1. Get all data into proper units

V = 27,000 L

oC + 273 = 298 K P = 745 mm Hg (1 atm/760 mm Hg) = 0.98 atm And we always know R, 0.0821 L atm / mol K 2. Now plug in those values and solve for the unknown. PV = nRT 4 (0.98 atm)(2.7 x 10 L) n = (0.0821 L . atm/K . mol)(298 K) n = 1.1 x 103 mol (or about 30 kg of gas)

T = 25

5.4. Gas Stoichiometry

Volume of 1 mole of an ideal gas at 0oC (273.2 K) and 1 atm:

V = nRT = (1.000 mol) (0.0821 L.atm/K.mol) (273.2 K) = 22.42 L P 1.000 atm This volume of 22.42 liters is the molar volume of an ideal gas (at 0oC and 1 atm). The conditions 0oC and 1 atm, called standard temperature and pressure (abbreviated STP)

Figure 5.11 22.42 L of a gas would just fit into this beach ball.

Practice problem
A sample of nitrogen gas has a volume of 1.75 L at STP. How many moles of N2 are present? Solution 1 mole of an ideal gas at STP has a volume of 22.42 L, 1.75 L N2 at STP will contain less than 1 mole. We can find how many moles using the ratio of 1.75 L to 22.42 L 1.75 L N2
=

1 mol N2 = 7.81 x 10-2 mol N2 22.42 L N2

Practice problem
2 H2O2 (l) ---> 2 H2O (g) + O2 (g) Decompose 1.1 g of H2O2 in a flask with a volume of 2.50 L. What is the volume of O2 at STP? Solution 1.1 g H2O2 1 mol H2O2 1 mol O2 22.4 L O2 34 g H2O2 2 mol H2O2 1 mol O2

= 0.36 L O2 at STP

What if its NOT at STP?

1. 2. Do the problem like it was at STP. (V1) Convert from STP (V1, P1, T1) to the stated conditions (P2, T2) P1V1 = P2V2 T1 T2

Try this one!

How many L of O2 are needed to react 28.0 g NH3 at 24C and 0.950 atm? 4 NH3(g) + 5 O2(g) 4 NO(g) + 6 H2O(g)

Molar Mass of a Gas

Number of mole of a gas:

m/V is the gas density d in units of grams per liter. Thus

5.4. Daltons Law of Partial Pressures

John Dalton 1766-1844

For a mixture of gases in a container, the total pressure exerted is the sum of the pressures that each gas would exert if it were alone.

 The partial pressure is the contribution by that gas. PTotal = P1 + P2 + P3+ For example: We can find out the pressure in the third container by adding up the pressure in the first 2. The volume remains constant.

What is the total pressure in a balloon filled with air if the pressure of the oxygen is 170 mm Hg and the pressure of nitrogen is 620 mm Hg? In a second balloon the total pressure is 1.3 atm. What is the pressure of oxygen if the pressure of nitrogen is 720 mm Hg?

Mole Fraction
The ratio of the number of moles of a given component in a mixture to the total number of moles in the mixture.

n1 n1 = = ntotal n1 + n2 + n3 + ... V n = P RT

V ( P1 + P2 + P3 + ...) RT P1 P 1 = = 1 ( P1 + P2 + P3 + ...) Ptotal P2 1 = Ptotal

1 =

n1 = ntotal

V P1 RT

Collecting Gas over Water

Gases, since they mix with other gases readily, must be collected in an environment where mixing can not occur. The easiest way to do this is under water because water displaces the air. So when a gas is collected over water, that means the container is filled with water and the gas is bubbled through the water into the container. The pressure inside the container is from the gas AND the water vapor. Example

Figure 5.13 The production of oxygen by thermal decomposition of KClO3. The MnO2 is mixed with the KClO3 to make the reaction faster.

A sample of solid potassium chlorate (KClO3) was heated in a test tube (see Fig. 5.13) and decomposed by the following reaction: 2KClO3(s) 2KCl (s) + 3O2(g) The oxygen produced was collected by displacement of water at 22oC at a total pressure of 754 torr. The volume of the gas collected was 0.650 L, and the vapor pressure of water at 22oC is 21 torr. Calculate the partial pressure of O2 in the gas collected and the mass of KClO3 in the sample that was decomposed. Solution Ptotal = PO2 + PH2O = PO2 + 21 torr = 754 torr PO2 = 754 torr 21 torr = 733 torr = 0.964 atm nO2 = PO2 (V/RT) V = 0.650 L T= 22oC + 273 = 295K R = 0.08206 L.atm/K.mol nO2= 2.59 x 10-2 mol Moles of KClO3 = 1.73 x 10-2 mol Mass of KClO3 = 2.12 g KClO3

5.6. The Kinetic Molecular Theory of Gases

Postulates of the Kinetic Molecular Theory 1. The particles are so small compared with the distances between them that the volume of the individual particles can be assumed to be negligible (zero). 2. The particles are in constant motion. The collisions of the particles with the walls of the container are the cause of the pressure exerted by the gas. 3. The particles are assumed to exert no forces on each other; they are assumed neither to attract nor to repel each other. 4. The average kinetic energy of a collection of gas particles is assumed to be directly proportional to the Kelvin temperature of the gas.

Pressure and Volume (Boyles Law)

Based on the KMT model, when the volume of a gas decreases, the gas particles hit the wall more often and thus increasing the pressure.

Pressure and Temperature

When the temperature of a gas increases, the speed of its particles increases and they will hit the wall harder resulting in increased pressure.

Volume and Temperature (Charless Law)

When a gas is heated to a higher temperature, its particles move at higher speed and hit the wall more often and with greater force. The only way to keep the gas pressure constant is to increase its volume.

Volume and Number of Moles (Avogadros Law)

An increase in the number of gas particles at the same temperature would cause the pressure to increase if the volume were held constant. The only way to return the pressure to its original value is to increase the volume.

Mixture of Gases (Daltons Law) The total pressure of a mixture of gases is the sum of the pressures of the individual gases is expected according to the KMT model which assumes all gas particles are independent of each other and their volume is negligibly small. The identities of gas particles are not important.

Deriving the Ideal Gas Law

By applying the principles of physics to the assumptions of the KMT, we can derive the ideal gas law.

Pressure A molecule bounces elastically off wall

Choose x-axis perpendicular to the wall The y- and z-components of momentum of the molecule are unchanged by the collision pi,x = -mvx pf,x = +mvx Change in momentum = pf,x pi,x = 2mvx Impulse = Change in momentum Impulse = average force times duration of collision. 2L/vx = Number of collisions per second with wall of box of size L.

 Force = Change in momentum per unit time F = [2mvx] / [2L/vx ]= mvx2 / L Pressure = Force per unit area = F/L2 = mvx2 / L3= m vx2 / V This is pressure from one molecule with x-component of velocity vx. Pressure on wall from one molecule is mvx2 / V Pressure from N molecules with mean-square velocity (vx2)av P = Nm(vx2)avg / V, N=nNA (n is number of mole, NA Avogadros number) No preferred direction in space: (vx2)avg = (vy2)avg = (vz2)avg =(1/3) (v2)avg
P= N21 2 m ( v )avg V32 1 nNA mv2 2 2 P= 3 V

1 mv2 represents the average kinetic energy of a gas particle 2 1 Average kinetic energy of 1 mole gas: (KE )avg = NA mv2 2

From postulate 4 the average kinetic energy of the particles in the gas sample is directly proportional to the temperature in kelvins.
1 T mv 2 2
PV =

1 T = k mv 2 2
PV 2 = kT n 3 PV = RT and n

2 n (KE )avg 3

2 If assign R = k then 3

(KE )avg = 2 RT

The Meaning of Temperature

(KE )avg

3 = RT 2

The Kelvin temperature is an index of the random motions of the particles of a gas, with higher temperature meaning greater motion.

Root Mean Square Velocity (vrms)

vrms = v2 v2 = 3RT NAm 3RT M NAm = M (mass of a mole of gas in kilograms)

vrms =

Example: Calculate the root mean square velocity for the atoms in a sample of helium gas at 25oC.

What do we know? T =25C + 273 = 298K R = 8.3145 J/K.mol What is the mass of a mole of He in kilograms?
M = 4.00 g 1kg = 4.00 10-3 kg / mol mol 1000g

What is the root mean square velocity for the atoms of He?
3 8.3145 v = rms

J ( 298K ) J K.mol = 1.86 106 kg kg 4.00 10-3 mol

J = kg.m2 / s2 2 6 kg.m = 1.36 103 m / s v = 1.86 10 rms kg.s2

Mean free path: The average distance a particle travels between collisions in a particular gas sample Path of one particle in a gas. Any given particle will continuously change its course as a result of collisions with other particles, as well as with the walls of the container.

Collisions among gas particles lead to a large range of velocities as the particles collide and exchange kinetic energy

vrms for oxygen gas at STP is approximately 500 m/s, but the actual distribution of molecular velocities for oxygen gas at STP.

The effect of temperature on the velocity distribution in a gas

A plot of the relative number of N2 molecules that have a given velocity at three temperatures. As the temperature increases, both the average velocity and the spread of velocities increase. Because the kinetic energy increases with temperature, it makes sense that the peak of the curve should move to higher values as the temperature of the gas is increased. The peak of the curve reflects the most probable velocity.

5.7. Diffusion and Effusion

Diffusion- The mixing process of gases. For example, perfume molecules spreading across the room. Effusion - the passage of a gas through a tiny orifice into an evacuated chamber. Both processes depend on the speed of the molecules

The effusion of a gas into an evacuated chamber

Grahams Law of Effusion

The rate of effusion and diffusion is inversely proportional to the square root of the molar mass of the molecules.
Rate of effusion for gas 1 M2 = Rate of effusion for gas 2 M1 (M1 and M2 represent the molar masses of the gases)

Kinetic energy of a gas particle = 1/2 mv2 ~ kT Bigger molecules move slower at the same temperature Bigger molecules effuse and diffuse slower

Exercise
Calculate the ratio of the effusion rates of hydrogen gas (H2) and uranium hexafluoride (UF6), a gas used in the enrichment process to produce fuel for nuclear reactors. Solution Molar mass of H2 is 2.016 g/mol Molar mass of UF6 is 352.02 g/mol

MUF Rate of effusion for H2 352.02 = = 13.2 = Rate of effusion for UF6 MH 2.016
6 2

 Does the kinetic molecular model fit the experimental results for the effusion of gases? The effusion rate for a gas depends directly on the average velocity of its particles.
M2 v rms for gas1 Rate of effusion for gas 1 = = = v rms for gas 2 Rate of effusion for gas 2 3RT M1
M2 3RT M1

Chem2A Co.

Diffusion

NH3 (g) + HCl (g)

NH4Cl (s)

MHCl Distance traveled by NH3 v rms for NH3 36.5 = = = = 1.5 Distance traveled by HCl v rms for HCl MNH 17
3

Experimentally observed ratio of less than 1.5 The velocities of HCl and NH3 molecules at 25oC are about 450 and 660 m/s, respectively. But it takes several minutes for the two gases to meet. NH3 and HCl molecules undergo many collisions with O2 and N2 molecules as they travel through the tube.

5.8. Real Gas

Ideal gases do not exist Molecules do take up space All matter has volume There are attractive forces Otherwise there would be no liquids Real gases behave like ideal gases When the molecules are far apart They take a smaller percentage of the space; Ignoring their volume is reasonable This happens at low pressures When molecules are moving fast. Molecules are not next to each other very long; Attractive forces cant play a role. At high temperatures far above boiling point.

Effect of Pressure
Plots of PV/nRT versus P for several gases (at 200 K) For an ideal gas, PV/nRT equals 1 under all conditions, but notice that for real gases, PV/nRT approaches 1 only at very low pressures (typically below 1 atm).

Effect of Temperature
Plots of PV/nRT versus P for nitrogen gas at three temperatures. The behavior of the gas appears to become more nearly ideal as the temperature is increased.

How can we modify the assumptions of the kinetic molecular theory to fit the behavior of real gases? Van der Waals equation 2 n Pobs + a ( V - nb ) = nRT a is a number that depends on how V much the molecules stick to each other
Corrected pressure, Pideal Corrected volume, Videal b is a number that determined by how big the molecules are nb is the volume of the gas particles Real gas particles interact with one other so the pressure they exert on the container wall is smaller than in the case theres no interactions. The numbers of interactions depend on square of number of particles, and thus the concentration of the gas

5.9. Characteristics of several real gases

Pideal

n = Pobs + a V

A low value for a reflects weak intermolecular forces among the gas molecules. The importance of intermolecular interactions H2 < N2 < CH4 < CO2

5.10. Chemistry on the Atmosphere

Paper assignment: Read this section and write a paper (about 1 page long) summarizing what you learn about Chemistry in the Atmosphere. Due May 7