1

THE GASEOUS STATE

Kinetic Theory of Gases an excellent model of gases 1. Gas molecules have negligible volume compared with space between molecules. - molecules are spread out 2. Gas molecules move. When they hit side of container they contribute to pressure. 3. All collisions are elastic. - molecules behave like billiard balls, not soggy softballs 4. Gas molecules have no attraction or repulsion for each other. - gas molecules dont know other molecules are around 5. The speed of the gas molecules is proportional to the temperature. - kinetic energy of gas is related to speed Higher temperature increases average speed
.55 0.5

298 K 398 K

0.4

f ( u , 2 , 298) f ( u , 2 , 398) f ( u , 2 , 2000) 0.2 0.3

2000 K

0.1

0 0

6 u

10

12 12

velocity

- The average velocity of the gas molecules increases as the temperature increases. - Note that a sample of gas molecules doesnt have just one speed; the speeds are a distribution.

2 Increased molar mass decreases average speed

4.5 4

SF6, 298 K

f ( u , 2 , 298) f ( u , 44 , 298) f ( u , 146 , 298) f ( u , 146 , 2000)

CO2, 298 K

SF6, 2000 K

H2, 298 K

0 0

2 u

4 4.5

velocity - The average velocity of the gas molecules decreases as the molar mass increases. - Heavier molecules need more energy to move. Kinetic theory of gases is able to explain many properties of gases. 1. Gases are compressible. 2. Gases have low densities. 3. Gases mix completely. 4. Gases fill container uniformly. 5. Gases exert pressure on side of container. 6. Gases flow easily (have low viscosity).

DIFFUSION AND EFFUSION

Diffusion is the transport of gases through space so that they mix completely. - Gasoline molecules from open gas can diffuse through room. - Diffusion rate of depends on speed on molecules. - Diffusion rate also depends on density of gas. - Higher density that molecules are closer together, smaller mean free path. - Smaller mean free path means more collisions. Effusion is the transport of gases thru a small pinhole. - Principles of effusions nearly the same as diffusion. - Kinetic theory explains diffusion of gases very well.

PRESSURE
Definition:

Force Area A square meter column of air weights 101,325 N. - 22,730 lbs. 101325 N Atmo. Pr ess. = = 101325 Pa = 101.325 kPa 1m 2 SI Unit of pressure is Pascal Pa Pr essure =

1 Pa = 1
Pressure is measured with a barometer.

N m2

vacuum (no air) pressure of Hg column atmospheric pressure

Hg pool

- Pressure of mercury column on surface of Hg pool balances atmospheric pressure pushing on Hg pool. - Height of column indicates atmospheric pressure. - At sea level, column of Hg is 760 mm (29.92 in.) - At sea level, column of H2O is 33.7 ft!! - see exhibit of atrium of DSC Relative pressures are measured with manometers. 1. Open-end manometer Mercury (or another dense fluid) is used to fill the tube. The end of the tube is exposed to atmospheric (laboratory) pressure.

System pressure is less than atmospheric pressure. psys + p Hg = p atm

System pressure is greater than atmospheric pressure. psys = patm + p Hg

4 2. Closed-end manometer The end of the tube is sealed from the atmosphere and pump to a vacuum.

vacuum System pressure cannot be directly compared to atmospheric pressure. psys = p Hg

UNITS OF PRESSURE
1.) Pascals (Pa) 2.) Atmospheres (atm) 3.) Torr or mmHg Must be able to convert between atmospheres and Torr (mmHg).

1atm = 760 Torr = 760 mmHg

Example: How many mmHg is 0.858 atm?

- aside: Lowest pressure of Typhoon Tip (1979) Example: How many atmospheres is 3.8 x 108 Torr?

- aside: Pressure at the center of the earth

BOYLES LAW
Pressure and volume of a gas are inversely proportional to each other, all other factors being constant (such as temperature and amount).

1 V

P=

k V

PV = k

P1 V1 = P2 V2

Consider cylinder with piston Pa - gas molecules inside cylinder hit piston and cylinder walls creating pressure

Pa

- initially pressure inside cylinder is atmospheric pressure, Pa

Now apply additional external pressure, Pex. - I.e., push down on piston.

Pext Pa
- pressure inside is greater - gas molecules hit walls more often - note volume is smaller

Pa Pext
Now pull out piston, to create lower pressure inside.

Pext Pa
- total pressue (pressure inside) is less than atmospheric pressure - volume of gas is larger

Pa Pext

Restating Boyles Law - as pressure increases, volume decreases - as pressure decreases, volume increases Example: A gas sample originally has a pressure of 900 Torr and a volume of 125 mL. If the temperature is constant, what is the pressure of the gas when it occupies 500 mL?

CHARLES LAW
Volume and temperature are proportional to each other, all other factors being constant. V V1 V2 V= kT =k VT = T T1 T2 As temperature decreases, volume decreases As temperature increases, volume increases **Must use temperature on Kelvin scale.** Consider a foil helium balloon - pressure inside is approximately atmospheric pressure

- taking balloon from room temperature to cold outside temperature (say 20 F), deflates balloon - temperature of gas decreases, therefore volume decreases - taking balloon back inside increases temperature, therefore volume increases Example: If the pressure and amount remain the constant, what is the new temperature of a gas initially at 3.6 L and 25 C, when the volume is changed to 4.8 L? Must use Kelvin temperatures.

AVOGADROS LAW
As the amount (in moles) increases, volume increases. As the amount (in moles) decreases, volume decreases. V V1 V2 V n V= k n =k = n n1 n 2 Consider cylinder with piston and air pump

air pump

7 Pumping air into cylinder increases volume.

air pump

Pumping air out of cylinder decreases volume.

air pump

IDEAL GAS EQUATION

Three quantities have been found to be proportional to the volume. Boyles Law
V 1 P

Charles Law VT Vn Avogadros Law All three of these proportionalities can be combined into one proportionality. nT V P Including a proportionality constant, the proportionality becomes an equation.

V=R

nT P

Rearranging equation into its most common form yields the Ideal Gas Equation. PV = nRT R is called the Ideal Gas Constant. R = 0.08206 Latm/molK Ideal gas constant is always the same. Note ideal gas equation has 4 variables. If we know 3 of the variables, we can solve for the fourth variable. Example: How many moles of gas are in a 2.0 L helium balloon at 25 C and at atmospheric pressure? PV = nRT Remember T must be in Kelvin. T = 25 C + 273 = 298 K

Rearrange ideal gas equation to solve for n.

8 Example: What is the volume of one mole of gas at standard temperature and pressure (STP)? Standard temperature = 0 C = 273 K Standard pressure = 1 atm Rearrange ideal gas equation to solve for V.

Ideal gas equation can be used to find ratios between two sets of conditions. - Use ideal gas equation to spot proportionality relationships. PV = nRT - Variables on opposite sides of equation are directly proportional. P1 P2 PT = T1 T2 - Variables on same side of equation are inversely proportional. 1 n n1T1 = n 2 T2 T Example: A constant amount of gas starts at 384 K, 63.2 L and 1.26 atm. What is the new pressure when the volume becomes 43.4 L and the temperature becomes 298 K? PV P1 V1 P2 V2 = nR = k PV= nRT = T T1 T2

Ideal gas equation can also be modified to calculate the molar mass of a gas. Reconsider density
d= m V

Mass can be rewritten in terms of molar mass and number of moles. m = n M Thus density can be rewritten

d=

nM V

Rearrange to solve for molar mass and substitute ideal gas equation.

M=d

RT V =d P n

or M =

mRT PV

However, the easiest method to understand is to apply the definition of molar mass directly. That is, to calculate the molar mass, find the mass of the gas and the number of moles of gas and divide moles into mass. m M= n

9 Example: 255 mL flask is filled with an unknown gas to a pressure of 745 Torr. The evacuated flask weighs 238.120 g. The filled flask weighs 239.092 g. The lab temperature is 22.0 C. Find the molar mass of the gas. mass of gas temperature 239.092 g 238.120 g = 0.972 g 22.0 C + 273.15 = 295.2 K

pressure P = 745 Torr

1atm = 0.980 atm 760 Torr

1L = 0.255 L 1000 mL

volume

V = 255 mL

moles of gas n =

PV 0.980 atm 0.255 L = = 0.0103mol RT 0.08206 L atm 295.2K mol K

M=

m 0.972 g = = 94.4 g / mol n 0.0103mol

APPLICATIONS IN STOICHIOMETRY
Since we can relate number of moles of gas to other properties of gases, we can relate ideal gas equation to stoichiometric properties. Example: What volume of SO2 (g) is produced at STP, when 10.0 g of sulfur burns with an excess of oxygen according to the reaction? S8 (s) + 8 O2 (g) 8 SO2 (g) ** Always compare moles to moles! ** - how many moles of SO2 are produced?

Now use ideal gas equation to convert moles to volume.

10 Example: How much NaN3 is needed to inflate a 50.0 L air bag to 1.15 atm given the following chemical reaction? 2 NaN3 (s) 2 Na (s) + 3 N2 (g) Assume temperature to be 25 C. First we need to know how many moles of N2 are in an inflated air bag. Use ideal gas equation.

Now use stoichiometry to find number of NaN3 grams.

DALTONS LAW OF PARTIAL PRESSURE

The total pressure of a system equals the sum of the pressures of the component gases that each would exert if they were alone. PT = P1 + P2 + P3 + P1, P2, P3, - partial pressures

- Gases behave as if they are not affected by other gas molecules. - This follows from the kinetic theory of gases. For air P(N2) = P(O2) = P(Ar) = + P(CO2) = P(total) = 0.781 atm 0.209 atm 0.009 atm 0.001 atm 1.000 atm total pressure equals sum of partial pressures

Example: 0.73 mol O2, 1.92 mol N2, 0.41 mol C2H6 are inside a 12.5 L container at 470 K. Calculate the partial pressure of each gas and the total pressure. Calculate partial pressures
L atm n R T 0.73 mol 0.08206 mol K 470 K = PO 2 = = 2.25 atm 12.5 L V L atm n R T 1.92 mol 0.08206 mol K 470 K = PN 2 = = 5.92 atm V 12.5 L L atm n R T 0.41 mol 0.08206 mol K 470 K PC 2 H 6 = = 127 atm . = V 12.5 L P(total) = P(O2) + P(N2) + P(C2H6) = 2.25 atm + 5.92 atm + 1.27 atm = 9.44 atm

11 Note if we sum of the moles of ideal gas first, then use the ideal gas equation to find the total pressure. n(total) = n(O2) + n(N2) + n(C2H6) = 0.73 mol + 1.92 mol + 0.41 mol = 3.06 mol
L atm n R T 3.06 mol 0.08206 mol K 470 K = 9.44 atm Ptotal = = 12.5 L V - note same answer as before - this is not a coincidence!

DEFINITION: Mole fraction

X1 =

n1 n1 = n n1 + n 2 + n 3 +

For previous example 0.73 mol 0.73 mol X O2 = = = 0.24 0.73 mol + 1.92 mol + 0.42 mol 3.06 mol 1.92 mol 0.42 mol XN2 = = 0.63 = 013 . X C2 H 6 = 3.06 mol 3.06 mol Sum of all mole fractions always equals one.

X O 2 + X N 2 + X C 2 H 6 = 0.24 + 0.63 + 0.13 = 1.00

Note that for gases in constant volume container, partial pressures can be used to find mole fractions.
n1 P1V / RT P1 = = P1 = X1P n PV / RT P - This equation is a restatement of Daltons Law ! X1 =

Note for oxygen in above example 2.25atm 2.25atm X O2 = = = 0.24 2.25atm + 5.92 atm + 1.27 atm 9.44 atm

12

COLLECTING GASES OVER WATER

The pressure that a liquid exerts on the atmosphere is called the vapor pressure. Molecules on surface of water have kinetic energy. Some of the molecules get enough kinetic energy to escape into gas phase. - pan of water at room temperature eventually evaporates. When collecting gases over liquid, the vapor pressure of the liquid will contribute to the total pressure of the gases. volume of gas

during reaction

reaction completed

- volume of gas includes partial pressure due to vapor pressure of water Example: 4.84 g of CaCO3 decomposes in a dilute HCl solution. The CO2 gas is collected over water into a volume of 1.16 L. The atmospheric pressure is 755 Torr. The temperature is 21 C. The vapor pressure of water is 18.65 Torr at 21 C. a) Find the number of moles of CO2 collected.
Ptotal = PCO2 + PH 2O = 755 Torr PCO2 = 755 Torr 18.65 Torr = 736 Torr

1atm . 116 L 760 Torr PV = 0.0466 mol = n= L atm RT 0.08206 294 K mol K 736 Torr
b) Calculate the percent yield CaCO3 (s) + 2 HCl (aq) CaCl2 (aq) + H2O (l) + CO2 (g) 1 mol CaCO 3 1 mol CO 2 4.84 g CaCO 3 = 0.0484 mol 100.09 g CaCO 3 1 mol CaCO 3
% yield = 0.0466 mol 100% = 96.2 % 0.0484 mol