GASES

Expand to fill and assume the shapes of their container Properties of Gases Colorless: O2, N2 Colored : Cl2 - greenish yellow Br2 - reddish brown I2 - violet Combustible: CH4, C3H8 Non-combustible: N2, Ar Unreactive: Ne, He

GASES
Physical behavior determined by:
Amount of gases - mole, mass, no. of particles Volume - space occupied by the gas molecules - mL, L, cm3, dm3 Temperature - Ave. K.E. of molecules of a gas - oC, oF, K = 273 + oC (absolute temperature) Pressure Force per unit area; P = F/A

GASES
Units of Pressure newton per square meter (N/m2) pascal (Pa) torr (torr) pounds per square inch (lbs/in2, psi) kg per square cm (kg/cm2) bar (bar) 1 atm 101,325 101,325 760 14.696 1.033 1.0132

Determine 1 property based on the other 3 properties by using mathematical equations called equations of state known as Gas Laws.

GASES
GAS LAWS natural laws governing the physical properties and behavior of gases. BOYLES LAW CHARLES LAW

AVOGADROS LAW

IDEAL GAS EQUATION

GASES
1. BOYLES LAW
Robert Boyle in 1662 (he used bent tubes with Hg)
For a fixed amount of gas at constant temperature, gas volume is inversely proportional to gas pressure.

P
P

1/ V
(k1) 1/ V k1 a constant

k1/ V

PV = k1

GASES
1. BOYLES LAW

PV = k1
Any P ~ V relationship results in a constant, k1 therefore; we can relate P & V in an initial condition (1) to P & V in a final condition (2)

P 2x, V 1/2
2

P 3x, V 1/3

P
1

V P1V1 = k1 P2V2 = k1

P1V1 = P2V2

GASES
SAMPLE PROBLEM (Boyles Law)

An inflated balloon has a volume of 0.55 L at sea level (1.0 atm pressure) and is allowed to rise to a height of 6.5 km, where the pressure is 0.40 atm. Assuming that the temperature remains constant, what is the volume in L of the balloon at that height?
Given: initial conditions V1 = 0.55 L; P1 = 1 atm final conditions P2 = 0.40 atm

Find:

V2 = ?

Solution: Use simple equations of state, Boyles Law:

P1V1 = P2V2

V2 = P1V1 P2

V2 = 0.55 L x 1.0 atm = 1.4 L 0.40 atm

GASES
2. CHARLES LAW
French physicist Jacques Charles in 1787 - showed the relationship between gas volume and temperature

The volume of a fixed amount of gas at constant pressure is directly proportional to the absolute temperature.

k2 T

V = (k2) T

V
T

k2 a constant

= k2

GASES
2. CHARLES LAW

V T

= k2
Any V~T relationship results in a constant, k2 therefore; we can relate V & T in an initial condition (1) to V & T in a final condition (2)

V (cm3)

T(K)

V1
T

V2
T2

1 T cannot be in oC because of -oC after 0oC so the relation cannot be directly proportional throughout the scale. The gas is also hypothetical (ideal) because real gases condense to liquids/solids before T approaches absolute 0 or 0 K

GASES
SAMPLE PROBLEM (Charles Law)

Argon is an inert gas used in light bulbs. If 452 mL of this gas is heated from 22oC to 187oC at constant pressure, what is the final volume?
Given: initial conditions final conditions

T1 = 22oC ; V1 = 452 mL Find: V2 = ?

Solution: T has to be converted to K

T2 = 187oC

Use simple equations of state, Charles Law:

T1 = 273 + 22oC = 295 K T2 = 273 + 187oC = 460 K

V1
T1

V2
T2
295 K

T2V1
T1

= V2

V2 = 452 mL x 460 K = 705 mL

GASES
BOYLES LAW
PV = k1
Combined Boyles and Charles Law:

CHARLES LAW
V
T P1V1 T1 = k2

For the same gas;

P2V2 T2

Since gas properties depend on To and P it is useful to have a reference or standard condition for To & P. Standard Temperature, T = 0 oC = 273.15 K Standard Pressure, P = 1 atm = 760 mm Hg STP = 273.15 K temperature and 1 atm pressure

GASES
SAMPLE PROBLEM (Combined Boyles and Charles Law)

A sample of diborane gas (B2H6), a substance that bursts into flames when exposed to air, has a pressure of 345 torr at a temperature of -15oC and a volume of 3.48 L. If the temperature is increased to 36oC and the pressure is 468 torr, what will be the volume in L?
Given: initial conditions final conditions

T1 = -15oC ; V1 =3.48 L; P1=345 torr Find: V2 = ?

T2 = 36oC; P2= 468 torr

Solution: Use combined Boyles & Charles Law:

P1V1 T1

P2V2 T2

P1V1T2 P2T1

= V2

GASES
SAMPLE PROBLEM (Combined Boyles and Charles Law)
Given: initial conditions final conditions

T1 = -15oC ; V1 =3.48 L; P1= 345 torr

Find:

T2 = 36oC; P2= 468 torr

V2 = ?

Solution: Use combined Boyles & Charles Law: To has to be converted first to K: T1 = 273 + (-15oC) = 258 K

T2 = 273 + 36oC = 309 K 345 torr 3.48 L 309 K 468 torr 258 K

= V2

V2= 3.07 L

GASES
3. AVOGADROS LAW
1808 Gay-Lussac reported that gases react by volumes in the ratio of whole numbers. - equal volumes of gases at the same To & P, contain equal number of atoms.
Dalton did not agree because he thinks that the reaction of hydrogen and oxygen in water would be: H(g) + O(g) HO (g) w/ a 1:1:1 proportion however the observed ratio is 2:1:1

GASES
3. AVOGADROS LAW
Amedeo Avogadro resolved the issue by proposing that: equal volumes of different gases compared at the same temperature and pressure contain equal number of molecules
equal number of molecules of different gases compared at the same temperature and pressure occupy equal volumes

At a fixed temperature and pressure, the volume of a gas is directly proportional to the amount of gas.

GASES
3. AVOGADROS LAW
At a fixed temperature and pressure, the volume of a gas is directly proportional to the number of moles of gas.

V
V

= k3 n

V
n

Any V~n relationship results in a constant, k3 therefore; we can relate V & n in an initial condition (1) to V & n in a final condition (2)

= k3

V1
n1

V2 n2

k3 a constant

GASES
3. AVOGADROS LAW
At STP, the volume occupied by 1 mole of gas with 6.02 x 1023 molecules is equal to 22.4 L Molar volume of a gas at STP = 22.4 L
Sample Problem: Propane gas, C3H8 is stored as liquid under pressure. The liquid vaporizes when the pressure is decreased (pressure is released). If 30.0 L of gas is released at STP, what is the mass of gas released? Given: V =30.0 L; STP: 273 K & 1 atm pressure Find: mass (g) of C3H8 Solution: 44 g = 58.9 g 30.0 L x 1 mol C3H8 x 1mol C3H8 22.4 L

GASES
IDEAL GAS EQUATION
A unifying equation that includes all gas variables and combines the constants (k1, k2 k3) into R the universal gas constant

PV = k1 V = k2 T V = k 3 n

PV = nRT
where: P = pressure in atm V = volume in L n = moles of gas T = temperature in K R = 0.0821 L .atm mol. K

GASES
IDEAL GAS EQUATION
Ideal Gas: - gas particles have no volume, no attraction for each other and in continuous motion, exerting pressure on its container by colliding with the walls.

Gases tend to behave ideally at high T & low P Gases tend to behave non-ideally at low T & high P

GASES
When are we going to use the simple gas laws, the combined gas equations or ideal gas equation?
In general, we use the ideal gas equation
when a single set of conditions is given. When given 2 sets of conditions, where you have an initial or a final condition or state, the combined or the single gas laws may be used.

Molar Volume of gases at STP uses the Ideal gas equation: conditions of P = 1 atm & T = 273 K

GASES
SAMPLE PROBLEM

What is the volume in liters occupied by 7.40 g of CO2 gas at STP?

Given: mass (g) CO2 =7.40 g; Find: V (L) STP: T = 273 K & P= 1 atm

Solution: single set of condition-STP; use, Ideal Gas Eqn. or simply the molar volume

VCO2 = 7.40 g CO2 x 1 mol CO2 x 22.4 L = 3.77 L

44 g 1 mol

GASES
SAMPLE PROBLEM What is the density of ammonia (NH3) at 752 mm Hg and 55 oC. Given: P = 752 mm Hg x 1 atm = 0.989atm 760 mm Hg T = 55 oC + 273 = 328K Find: D (g/L) Solution: single set of condition, use Ideal Gas Eqn.

PV = nRT
D = m ; n = mass ; D = m = PMM; V MM V RT D = 0.989 atm x 17g mol-1 __ = (0.0821 L-atm mol-1 K-1) 328 K 0.62 g L

GASES
DALTONS LAW OF PARTIAL PRESSURES
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.

For a mixture of non-reacting gases A, B, C

Ptot = PA + PB + PC +
Assuming that each gas behaves ideally, the partial pressures of each gas could be expressed as in an ideal gas equation:

nA PA VA n tot Ptot Vtot

GASES
DALTONS LAW OF PARTIAL PRESSURES
SAMPLE PROBLEM

What is the partial pressure of Cl2(g) in mm Hg, in a gaseous mixture at STP that consists of 46.5% N2, 12.7% Ne & 40.8% Cl2 by mass? Assume 100 g of gas mixture, convert % composition
to grams Given: % Comp. 46.5% N2 12.7% Ne 40.8% Cl2 Mass (g) 46.5 g N2 12.7 g Ne 40.8 g Cl2 STP:

273 K
1 atm or 760 mm Hg

GASES
DALTONS LAW OF PARTIAL PRESSURES
SAMPLE PROBLEM (contd) Mass in g of each gas convert to mol of each gas; nCl2, nN2, nNe 40.8 g 46.5 g 12.7 g nCl = 2 nN2= nNe= 70.9 g/mol 28 g/mol 20.2 g/mol nN2= 1.66 mol nNe= 0.628 mol nCl2= 0.575 mol
Get total number of moles ntot for all gases

ntot = 1.66 mol + 0.628 mol + 0.575 mol = 2.86 mol

Use Daltons law of partial pressures; nCl2 = P0Cl2 P0Cl2 = nCl2 x Ptot ntot Ptot ntot

GASES
DALTONS LAW OF PARTIAL PRESSURES
SAMPLE PROBLEM (contd)

P0Cl2 = nCl2 x Ptot = 0.575 mol x 760 mmHg ntot 2.86 mol P0Cl2 = 153 mmHg

GASES
NON-IDEAL GASES (REAL GASES)
show behavior deviating from ideal gases at high pressures, molecules become crowded and repulsive forces among electrons does not allow volume of gas to approach zero. At high pressures compression and crowding allow for IMFA to be effective, therefore pressure of real gases decrease since collision with walls are decreased as a result of IMFA.
For real gases, van der Waals equation:
Ideal gas equation corrected for: P+ V nb = nRT volume of molecules 2 V IMFA effect on pressure a & b are specific values for particular gases

n2a

GASES
Kinetic Molecular Theory
a gas is composed of very large number of extremely

small particles in constant random, straight-line motion molecules are separated by great distances molecules collide with one another and with the walls of their container. These collisions occur very rapidly, however, most of the time they are not colliding. There are assumed to be no forces between molecules except very briefly during collisions. Individual molecules may gain or lose energy as a result of collisions. In a collection of molecules at constant temperature, the total energy remains constant.

GASES
Kinetic Molecular Theory
Kinetic Molecular Eqn. :

N 2 1 P= mu 3V

where: m - mass of molecule; N - # of molecules present in a volume, V u 2- average of the squares of molecules speed

GASES
DIFFUSION AND EFFUSION
properties related to kinetic molecular theory

rates at which diffusion and effusion occur are directly proportional to molecular speed.
DIFFUSION migration or intermingling of molecules of different substances as a result of random molecular motion. EFFUSION escape of gas molecules from their container through a tiny hole (pin hole). rms = root mean square speed = square root of the average of the
squares of the speeds of all molecules in a sample.

3RT rms MM

R ~ 8.3145 kgm2s-2mol-1K-1

GASES
DIFFUSION AND EFFUSION
Effusion of 2 different gases at the same To and P Grahams Law the rates of effusion (or diffusion) of 2 different gases are inversely proportional to the square root of their molar masses. Rate of effusion of A ( r ms)A 3RT/MMA MMB __________________ = ________ = ________ = ___ Rate of effusion of B ( r ms)B 3RT/MMB MMA

molecules with smaller mass have higher speed (r ms) lighter gas effuses faster than heavier gas gas that effuses fastest travels farthest at a given time

GASES
DIFFUSION AND EFFUSION
Rate of effusion of A MMB __________________ = _____ Rate of effusion of B MMA

Generalize the above equation to:

ratio of: 1. 2. 3. 4. 5. molecular speed rates of effusion effusion times distance traveled amount of gas effused

ratio of 2 MM

GASES
DIFFUSION AND EFFUSION
SAMPLE PROBLEM
If 2.2 x 10-4 mol of N2(g) effuses in 105 s, how much He(g) would effuse through a tiny hole in the same period of time?
Given: Amt. of N2 effused = 2.2 x 10-4 mol Find: Amt. of He effused Solution: Effusion time = 105 s

1. using Grahams Eqn., analyze qualitatively to decide the sequence of the MM ratio.
Amt of He effused = MMHe = 4 g/mol

Amt. of He effused _________________ = Amt. of N2 effused

MMHe orN2 _____ MMHe orN2

MMN2 He x Amt of N2 effused MMHe N2 MMN2 = 28 g/mol

or

28

GASES
DIFFUSION AND EFFUSION
SAMPLE PROBLEM (contd)
2. substitute given values and solve. Amt of He effused = 28 4 Amt of He effused = 5.8 x 10-4 mol x 2.2 x 10-4 mol

How much O2 would effuse in the same orifice at the same period of time? MMO2= 32 g/mol How long would it take for 2.2 x 10-4 mol He(g) to effuse through the same orifice?