10/25/07

Zumdahl Chapter 5: Gases

Gaseous state is easiest to describe experimentally and theoretically
Provides example of scientific method in action
Illustrates how observations lead to natural laws/models
Earths atmosphere primarily elemental nitrogen/oxygen
Supports life; acts as waste receptacle for exhaust gases
5.1: Early Experiments
Jan Baptista Ban Helmont: first person to attempt scientific study of the vapors produced by
chemical reactions
Thought air was similar to chaos the universe created, according to Greek myth,
therefore named them after Flemish word for chaos gas
Evangelista Torricelli performed experiments that showed that the air in the atmosphere
exerts pressure
Designed the first barometer by filling a tube closed at one end w/ mercury and then
inverting it in a dish of mercury
A column of mercury approx. 760mm long always remained in tube from atmospheric
pressure
Otto von Guericke: invented an air pump (vacuum pump)
Placed 2 hemispheres together and pumped air out; horses couldnt pull them apart, but
once he filled w/ air again, he could pull apart
Units of Pressure
Most instruments use mercury because of its high density
mm Hg is called the torr for Torricelli
Standard atmosphere: 1 standard atmosphere = 1 atm = 760 mm Hg = 760 torr
Pressure = force/area
Units in SI system are newton (N)/square meters (m^2)
Pascal (pa); 1 standard atmosphere = 101,325 Pa
5.2: The Gas Laws of Boyle, Charles, and Avogadro
Boyles Law
Used a J-shaped tube closed at one end
Studied relationship between pressure of the trapped gas and its volume
Product of the pressure and volume for the trapped air sample is constant
Boyles Law: PV=k; k is a constant at a specific temp. for a given air sample
Plot P vs. V
Produces a hyperbola; pressure drops by half, the volume doubles
Inverse relationship between pressure and volume
V=k/P (equation for a straight line of the type y=mx+b)
y=v; x=1/P; m=k; b=0
Plot gives straight line with intercept of zero
An approximation of the relationship between pressure and volume for a gas
Small changes that occur in the product PV as the pressure is varied
Very significant at pressures much higher than normal atmospheric temps.
Ideal gas: a gas that obeys Boyles Law.
Law used to predict new volume of gas when pressure is changed (at constant temp.)/vise versa

Charles Law
Jacques Charles; first person to fill a balloon w/ hydrogen gas/made first solo balloon flight
Volume of gas at a constant pressure increases linearly w/ temperature of gas
Plot volume of gas vs. temperature deg. C
Volumes of all gases extrapolate to zero at the same temperature (-273.2 C)
Temperature (K) = 0 deg. C + 273
Plot volume of gas vs. temperature K
Volume of each gas is directly proportional to temperature/extrapolates to 0
Charles Law: V=bT; T is temp in K, b is proportionality constant
Absolute zero: zero degrees K; temp. cannot be attained
Avogadros Law
Postulated that equal volumes of gases at the same temp./pressure contain the same number of
particles.
Avogadros Law: V=an; v is volume of gas, n number of moles, a a proportionality 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
Universal gas constant: R is the combined proportionality constant.
R=.08206 L atm K^-1 Mol^-1
When pressure in atm and volume in L
Ideal gas law: PV=nRT
An equation of state for a gas where the state of the gas is its condition at a given time
A particular state of gas is described by its pressure, volume, temp. and # of moles
Empirical equation based on experimental measurements of the properties of gases
Gas that obeys this equation is said to act ideally
Limiting law it expresses behavior that real gases approach at low pressures/high temp.
Most gases obey this equation closely enough at pressures below 1 atm
Often used to calculate the changes that will occur when conditions are changed
P1V1=nRT=P2V2
P1V1=P2V2 V1/T1=V2/T2
(P1V1/T1)=(P2V2/T2)
5.4: Gas Stoichiometry
Molar volume of an ideal gas: volume of 22.42 liters (@STP)
Can carry out stoichiometric calculations if pressure, volume and temp. are known
Molar Mass
n = grams of gas = mass = m
molar mass molar mass molar mass
OR molar mass = dRT/P
Can calculate molar mass if density of a gas at a given temperature and pressure is known
5.5: 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.
Daltons law of partial pressures: P total = P1 + P2 + P3 +
Partial pressures: pressure that gas would exert if it were alone in the container
P1=n1RT/V
Pressure exerted by an ideal gas is not affected by the identity (structure) of gas particles
Volume of individual gas particles must not be important
Forces among the particles must not be important

Mole Fraction: the ration of the number of moles of a given component in a mixture to the
total number of moles in the mixture.
X1= n1/ntotal
X1=P1/Ptotal
P1=X1xPtotal
The partial pressure of a particular component of a gaseous mixture is equal to the mole
fraction of that component times the total pressure.
Vapor pressure of water: (depends on temperature) When the rate of escape equals rate of
return, the number of water molecules in the vapor state remains constant, and thus the
pressure of water vapor remains constant.
5.6: The Kinetic Molecular Theory of Gases
Model considered successful if it explains the observed behavior in question and predicts
correctly the results of future experiments
A model can never be proved to be absolutely true
Any model is an approximation by its very nature and is bound to fail at some point
Kinetic molecular theory: a simple model that attempts to explain the properties of an ideal
gas.
Based on speculations about behavior of individual gas particles
An ideal gas consists of particles that have the following properties:
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).
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.
The particles are assumed to exert no forces on each other; they are assumed to
neither attract nor repel each other.
The average kinetic energy of a collection of gas particles is assumed to be directly
proportional to the Kelvin temperature of the gas.
The Quantitative Kinetic Molecular Model
Elastic collision: no loss of kinetic energy occurs.
(Collision frequency)x = velocity in the x direction = ux
distance between the walls L
F= mu/t = (mu)/t
mu is momenturm (mass times velocity)
Exact reversal: when a particle hits the wall, the x component of velocity chages; sign, or
direction of Ux reverses.
Final momentum is negative
Change in momentum = (mux) = final momentum initial momentum = -2(mux)
Total Forcex on box = 2(mux)^2/L + 2(muy)^2/L + 2(muz)^2/L = (2m/L)(u^2)
Kinetic energy = 1/2 mu^2
PV/n=RT from experiment; PV/n T from theory
The Meaning of Temperature
Kelvin temperature is a measure of the average kinetic energy of gas particles
(KE)avg. = 3/2 RT
The higher the temperature, but more motion of the particles
Root Mean Square Velocity

urms = sqroot(u^2 w/ line above it)

urms = sqroot(3RT/M)
M= number of particles in a mole x mass in kg = mass of a mole of gas particles (kg)
Joule: a kg m^2/s^2
R= 8.3145 J K^-1 mol^-1
Mean free path: the average distance a particle travels between collisions in a particular gas
sample; usually a very small distance
Many collisions among gas particles produce a large range of velocities
Maxwell-Boltzmann distribution law: distribution of velocities of the particles in an ideal gas
f(u)=4(m/2kBT)3/2u2e-mu2/2kBt
u = velocity in m/s
m = mass of a gas particle in kg
kB = Boltzmanns constant = 1.38066x10^-36 J/K
T = temperature in K
Product of f(u)du represents fraction of gas molecules w/ velocities between u and u+du
Equation for the most probably velocity
Ump = sqroot(2kBT/m) = sqroot(2RT/M)
M- molar mass of gas particles in kg=6.022x10^23 x m
R= gas constant = 6.022x10^23xkB
uavg = sqroot(8kBT/m) = sqroot(8RT/M)
ump:uavg:urms =1.000:1.128:1.225
5.7: Effusion and Diffusion
Diffusion: rate of the mixing of gases.
Effusion: term used to describe the passage of a gas through a tiny orifice into an evacuated
chamber; rate of effusion measures the rate at which the gas is transferred into the chamber.
Effusion
Thomas Graham
Rate of effusion of gas is inversely proportional to the square root of the mass of its particles
Grahams Law of Effusion
Rate of effusion for gas 1 = sqroot(M2)
Rate of effusion for gas 2 sqroot(M1)
M1 and M2 represent the molar masses of gases
Diffusion
Demo where cotton plugs (1 w/ ammonia, 1 w/ HCl) placed at either end of a long tube
Molecules suffer collisions w/ N2 and O2 molecules in the air
Gaseous diffusion: chambers separated by semi porous walls that allow passage of some
molecules but prevent bulk flow of gas.
5.8: Collisions of Gas Particles with the Container Walls
ZA collision rate (per second)
Section of wall that has an area A (m2)
ZA depends on:
1. The average velocity of the gas particles
2. The size of the area being considered
3. The number of particles in the container
N/V represents the number of particles N divided by volume (in m3)
ZA = (1/4)(N/V)(A)sqroot(RT/2M)

5.9: Intermolecular Collisions

Collision rate (per second) = Z = 4(N/V)(d2)sqroot(RT/M)
Mean Free Path
= 1/(sqroot(2)(N/V)(d2))
5.10: Real Gases
No gas exactly follows the ideal gas law.
Behavior approached by real gases under certain conditions.
Plot of PV/nRT vs. P
For an ideal gas PV/nRT equals 1 under all conditions
A real gas typically exhibits behavior that is closest to ideal behavior at low pressures and
high temperatures
The volume actually available to a given gas molecule is given by V-nb
n is number of moles; b is empirical constant
When gas particles are close together they are attracted and therefore hit the wall less
van der Waals equation: [Pobs + a(n/V)2](V-nb) = nRT
At high temperatures the effects of interparticle interactions are not very important
Particles are moving rapidly
5.11: Chemistry in the Atmosphere
Atmosphere: surrounds earths surface
Principle components are N2 and O2
Composition not constant due to gravity
Heavier molecules tend to be near earths surface/light molecules migrate higher up
Chemistry in higher levels of atmosphere due to high-energy radiation/particles from sun
Upper atmosphere shields up from harmful radiation
Chemistry in troposphere (lower level) is influenced by human activities
Severe air pollution causing long term changes
Main sources are transportation and production of electricity
Combustion of petroleum produce CO, CO2, NO, NO2
NO2 NO + O
O + O2 O3 ozone
Photochemical smog: called this because light is required to initiate some reactions
NO2 NO + O
O + O2 O3
NO + 1/2 O2 NO2
3/2 O2 O3
Combating this by trying to cut down on amounts of molecules from unburned fuel
and creating engines that produce less nitric oxide
Burning coal (to produce electricity) is a large source of pollution
S (in coal) + O2 SO2
2SO2 + O2 2SO3
SO3 + H2O H2SO4
Sulfuric acid is very corrosive.
As petroleum supply dwindles, dependence on coal will increase
Can remove the sulfur dioxide from the exhaust gas w/ a system called a scrubber
Blows powdered limestone (CaCO3) into combustion chamber where it is decomposed
CaCO3 CaO + CO2 the lime then combines w/ the sulfur dioxide to form CaSO3

CaO + SO2 CaCO3

Disadvantages to scrubbing
Systems are complicated/expensive
Consume a lot of energy
CaCO3 must be buried in a landfill
Acid Rain: causes freshwater lakes to become too acidic for fish to live.
H2O + CO2 H+ + HCO3NO2 and SO2 can produce higher H+ concentrations
Trees sick, lakes dying and building deteriorating
Experimenting w/ coating marble to protect it
Must allow water to pass through it or marble will crack