Chapter 10

GASES Aim: Examine the physical characteristics of gases and the transformations that occur among them CONTENTS: 10.1- Characteristics of Gases 10.2- Pressure 10.3- Gas Law 10.4- Ideal Gas Equation 11.5- Further Application of the Ideal-Gas Equation 10.6- Gas Mixtures and Partial Pressures 10.7- Kinetic Molecular Theory 10.8- Molecular Effusion and Diffusion 10.9 Real Gases:Deviation from Ideal Behavior

10.1 Characteristics of Gases: Gases are highly compressible and occupy the full volume of their containers When a gas is subject to an increasing pressure, its volume decreases Gases always form homogeneous mixture with other gases. 10.2 Pressure: Pressure = force/area : F/S = m/ S is the acceleration Unit: kg.m/s2.m2 or N/m2 SI unit: Pascal (1 Pa = 1 N/m2)
Units of Pressure 1 pascal (Pa) 1 atmosphere (atm) 1 atmosphere (atm) 1 bar 1 N*m-2 = 1 kg*m-1*s-2 1.01325*105 Pa 760 torr 105 Pa

Atmospheric Pressure and the Barometer : Due to earth gravity, the atmosphere exerts a pressure on the Earthsurface . Atmospheric pressure can be measured by a mercury barometer.

1 atm = 760 mmHg = 760 torr = 101,325 Pa Open end Manometer: U-shaped tubes containing mercury

Pgas= Patm - P

Pgas= Patm + P

10.3 Gas Law Four variables are usually sufficient to define the state (i.e. condition) of a gas:

Temperature, T Pressure, P Volume, V Quantity of matter, usually the number of moles, n

The equations that express the relationships among P, T, V and n are known as the gas laws The Pressure-Volume Relationship: Boyle's Law Robert Boyle (1627-1691) Studied the relationship between the pressure exerted on a gas and the resulting volume of the gas. He utilized a simple 'J' shaped tube and used mercury to apply pressure to a gas:

He found that the volume of a gas decreased as the pressure was increased Doubling the pressure caused the gas to decrease to one-half its original volume

Boyle's Law:
The volume of a fixed quantity of gas maintained at constant temperature is inversely proportional to the pressure

The value of the constant depends on the temperature and the amount of gas in the sample A plot of V vs. 1/P will give a straight line with slope = constant

The Temperature-Volume Relationship: Charles's Law

The relationship between gas volume and temperature was discovered in 1787 by Jacques Charles (1746-1823)

The volume of a fixed quantity of gas at constant pressure increases linearly with temperature

The line could be extrapolated to predict that gasses would have zero volume at a temperature of -273.15C (however, all gases liquefy or solidify before this low temperature is reached In 1848 William Thomson (Lord Kelvin) proposed an absolute temperature scale for which 0K equals -273.15C In terms of the Kelvin scale, Charles's Law can be restated as:

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

Doubling the absolute temperature causes the gas volume to double

The value of constant depends on the pressure and amount of gas

The Quantity-Volume Relationship: Avogadro's Law The volume of a gas is affected not only by pressure and temperature, but by the amount of gas as well.

Avogadro's hypothesis: Equal volumes of gases at the same temperature and pressure contain equal numbers of molecules 1 mole of any gas (i.e. 6.02 x 1023 gas molecules) at 1 atmosphere pressure and 0C occupies approximately 22.4 liters volume

Avogadro's Law: The volume of a gas maintained at constant temperature and pressure is directly proportional to the number of moles of the gas

Doubling the number of moles of gas will cause the volume to double if T and P remain constant

10.4- The ideal Gas Equation Summarizing the gas laws -Boyles law: V ~ 1/P (at constant T and n) -Charles law: V~ T (at constant n and P) -Avogadro law: V~ n (at constant T and P) The combination of those equations give a general gas law: V~ nT/P if R is the proportionality constant :

Ideal gas law or equation of state for an ideal gas:

PV = nRT
Where: P=pressure in atm T=temperature in kelvins R is the molar gas constant, where R=0.082058 L*atm*mol-1*K-1. The Ideal Gas Law assumes several factors about the molecules of gas. The volume of the molecules is considered negligible compared to the volume of the container in which they are held. We also assume that gas molecules move randomly an the attractive and repulsive forces between the molecules are considered negligible. Combined Gas Law:

Example Problem: A 25.0 mL sample of gas is enclosed in a flask at 22 degrees celsius. If the flask was placed in an ice bath at 0 degrees celsius, what would the new gas volume be if the pressure is held constant?

10.5 Further Application of Ideal-Gas Equation

The ideal gas law can be used to determine the density of a gas ,the molar mass, or the volumes of gases. From n = PV/RT m = M PV/RT where M is the molar mass , the density is d = m/V = P M /RT
Example Problem: A gas exerts a pressure of 0.892 atm in a 5.00 L container at 15 degrees celsius. The density of the gas is 1.22 g/L. What is the molecular weight of the gas?

Gas Mixtures and Partial Pressures

What happens when several gases are mixed in one container?

Dalton Law: the total pressure exerted on a container by several different

gases, is equal to the sum of the pressures exerted on the container by each gas.

Where: Pt=total pressure in atm P1=partial pressure, in atm, of gas "1" P2=partial pressure, in atm, of gas "2" and so on

assume that each gas is ideal and behaves independently of others.

. We

Where: X1=mole fraction of gas "1"

The partial pressure of each the gas in the mixture is equal to the total pressure multiplied by the mole fraction. Example Problem: A 10.73 g sample of PCl5 is placed in a 4.00 L flask at 200 degrees celsius. a) What is the initial pressure of the flask before any reaction takes place? b) PCl5 dissociates according to the equation: PCl5(g) --> PCl3(g) + Cl2(g). If half of the total number of moles of PCl5(g) dissociates and the observed pressure is 1.25 atm, what is the partial pressure of Cl2(g)?

Collecting Gases Over Water Example: Decomposition of CaCO3 in presence of Concentrated solution of HCl

CaCO3

HCl

Beaker

CaCO3(s) + 2 HCl CaCl2 + CO2(g) + H2O PT = pCO2 + pH2O = Patm

10.7 Kinetic Molecular Theory

Theoretical model to explain the behavior of ideal gases

Postulates :
1.Gases are composed of particles that are in constant, random motion. 2.Volume of individual molecules is negligible compared to the volume of the container. 3. intermolecular forces are negligible.

4. Each molecule has different energy.

5.The average kinetic energy of the particles is proportional to the absolute temperature.

10.8 Molecular Effusion & Diffusion The average kinetic energy of a gas is related to its mass : E= 1/2 mu2 where u is root mean square (rms) u = (3RT/ M)1/2
Grahams Law of Effusion: The shape of a gas is determined entirely by the container in which the gas is held. Sometimes, however, the container may have small holes, or leaks. Molecules will flow out of these leaks, in a process called effusion.

Effusion: is the escape of gas through tiny hole. Thomas Graham (1830):
Because massive molecules travel slower than lighter molecules, the rate of effusion is specific to each particular gas. We use Graham's law to represent the relationship between rates of effusion for two different molecules .

Where: r1=rate of effusion in molecules per unit time of gas "1" r2=rate of effusion in molecules per unit time of gas "2" u1=molecular mass of gas "1" u2=molecular mass of gas "2"

For instance a balloon filled with helium deflates more rapidly than ballon filled with air

Diffusion
Diffusion: the spread of one substance throughout a space, or a second substance . Diffusion is faster for lighter molecules. Diffusion is slowed by gas molecules colliding with each other

10.9 Real Gases: Deviation From Ideal Behavior

An ideal gases are those that fit the assumptions of the ideal gas law:

Ideal gas molecules are: abstract points without volume. no attractive forces. Real gas molecules: actual molecules (occupy space). attract each other.
When pressure is high or temperature is low, gases deviate farther from the ideal state. To account for these changes, a common equation used to better represent a real gas is the van der Waals equation:

a accounts for molecular attraction a (L2.atm/mol2) is proportional to the strength of the attractive forces. b accounts for volume of molecules . b (L/mol) is a measure of the actual volume occupied by the molecules

a (L2.atm/mol2)

b (L/mol)

He O2 NH3 H2O CH4 C2H6 CH3OH C2H5OH

0.034 1.36 4.17 5.46 2.25 5.489 9.523 12.02

0.0237 0.0318 0.0371 0.0305 0.0428 0.06380 0.06702 0.08407

The table below shows values for a and b of several different compounds and elements.

(P+ an2/V2) ( V-nb) = nRT Presence of 2 correction terms:

Previously, we considered only ideal gases, those that fit the assumptions of the ideal gas law. Gases, however, are never perfectly in the ideal state. All atoms of every gas have mass and volume. When pressure is low and temperature is high, gases behave similarly to gases in the ideal state. When pressure and temperature increase, gases deviate farther from the ideal state. We have to assume new standards, and consider new variables to account for these changes. A common equation used to better represent a gas that is not near ideal conditions is the van der Waals equation, seen below.

Where the van der Waals constants are: a accounts for molecular attraction b accounts for volume of molecules The table below shows values for a and b of several different compounds and elements. Species Helium Hydrogen Nitrogen Oxygen Benzene a (dm6*bar*mol-2) b (dm3*mol-1) 0.034598 0.24646 1.3661 1.3820 18.876 0.023733 0.026665 0.038577 0.031860 0.11974