Chapter 5: Gases and the

Kinetic - Molecular Theory

5.1 An Overview of the Physical States of Matter
5.2 Gas Pressure and its Measurement
5.3 The Gas Laws and Their Experimental Foundations
5.4 Further Applications of the Ideal Gas Law
5.5 The Ideal Gas Law and Reaction Stoichiometry
5.6 The Kinetic - Molecular Theory: A Model for Gas
Behavior
5.7 Real Gases: Deviations from Ideal Behavior
Important Characteristics of Gases
1) Gases are highly compressible
An external force compresses the gas sample and decreases its
volume, removing the external force allows the gas volume to
increase.
2) Gases are highly thermally expandable
When a gas sample is heated, its volume increases, and when it is
cooled its volume decreases.
3) Gases have low viscosity
Gases flow much easier than liquids.
4) Most gases have low densities
Gas densities are on the order of grams per liter whereas liquids
and solids are grams per cubic cm, 1000 times greater.
5) Gases are infinitely miscible
Gases mix in any proportion such as in air, a mixture of many gases.
Helium He 4.0
Neon Ne 20.2
Argon Ar 39.9
Hydrogen H
2
2.0
Nitrogen N
2
28.0
Nitrogen Monoxide NO 30.0
Oxygen O
2
32.0
Hydrogen Chloride HCl 36.5
Ozone O
3
48.0
Ammonia NH
3
17.0
Methane CH
4
16.0
Substances that are Gases under
Normal Conditions (300 K 1 atm)
Substance Formula MM(g/mol)
Important variable that describe a gas are
pressure (P), temperature (T), and volume (V)
Temperature is a measure of the kinetic energy of the gas
atoms or molecules
Pressure arises from collisions of the gas atoms or molecules
with the container walls
Chapter 5: Gases and the
Kinetic - Molecular Theory
5.2 The Gas Laws of Boyle, Charles, and Avogadro
5.3 The Ideal Gas Law
5.4 Gas Stoichiometry
5.5 Daltons Law of Partial Pressures
5.6 The Kinetic - Molecular Theory of Gases
5.7 Effusion and Diffusion
5.8 Collisions of Gas Particles with Container Walls
5.9 Intermolecular Collisions
5.10 Real Gases
5.11 Chemistry in the Atmosphere
Gas pressure can
be measured
using a
manometer
760 mm Hg =
1 atm
Magdeburg spheres
Boyles Law: At constant T, the product PV for a
given amount of a gas is constant
CHARLESS LAW: V/T = constant
if P, n held constant
Basis for absolute
temperature scale
T(K) = T(C) +273.15
Higher T (a higher KE) yields higher gas velocity, raising
P
gas
initially until top wall moves, which increases V until
P
gas
= P
atm
.
AVOGADROS
LAW:
V/n = constant
at constant T, P
Moles gas in B is
double that in A
so V is double
Ideal Gas Law
An ideal gas is defined as one for which both the
volume of molecules and forces between the
molecules are so small that they have no effect on
the behavior of the gas.
Independent of substance! In the limit that P 0,
all gases behave ideally
The ideal gas law is:
PV=nRT T is in kelvin
R = ideal gas constant = 8.314 J / mol K = 8.314 J
mol
-1
K
-1
R = 0.08206 L atm mol
-1
K
-1
The Ideal Gas Law Subsumes the Other Gas Laws
-- for a fixed amount at constant temperature
PV = constant PV = nRT
Boyles Law
for a fixed amount at constant volume
P increases linearly with T P = (nR/V)T
Amontons Law
for a fixed amount at constant pressure
V increases linearly with T V = (nR/P)T
Charless Law
for a fixed volume and temperature
P increases linearly with n P = (RT/V)n
Avogadros Law
Standard Temperature and Pressure (STP)
A set of Standard conditions have been chosen to make it easier to
understand the gas laws, and gas behavior.
Standard Temperature = 0
0
C = 273.15 K
Standard Pressure = 1 atmosphere = 760 mm Hg (Mercury)
or 760 torr
At these standard conditions, 1.0 mole of a gas will occupy a
standard molar volume of 22.4 L.
Many gas law problems involve a change of
conditions, with no change in the amount of gas.
= constant Therefore, for a change
of conditions :
T
1
T
2
P x V
T
P
1
x V
1
=
P
2
x V
2
EP100: Change of Three Variables - I
A gas sample in the laboratory has a volume of
45.9 L at 25.0
o
C and a pressure of 743 mm Hg.
If the temperature is increased to 155
o
C by
compressing the gas to a new volume of 31.0 L
what is the pressure in atm?
P
1
= 743 mm Hg x1 atm/ 760 mm Hg=0.978 atm
P
2
= ?
V
1
= 45.9 L V
2
= 31.0 L
T
1
= 25.0
o
C + 273 = 298 K
T
2
= 155
o
C + 273 = 428 K
1 1 2 2
1 2
PV PV
T T
=
2
2
31.0 L 0.978 atm 45.9 L
298 K 428 K
428 K 0.978 atm 45.9 L
298 K 31.0 L
P
P

= =

2.08 atm
EP101: Gas Law
Calculate the pressure (in atm) in a container filled with 5.038 kg of
xenon at a temperature of 18.8
o
C, whose volume is 87.5 L.
Strategy:
(1)Convert all information into the units required, and
(2)substitute into the ideal gas equation.
T = 18.8
o
C + 273.15 K = 292.0 K
Xe
5038 g Xe
n = 38.37 mol Xe
131.3 g Xe / mol
=
38.37 mol 0.0821 L atm 292.0 K
87.5 L
nRT
P
V

= = = 10.5 atm
EP102: Sodium Azide Decomposition - I
Sodium azide (NaN
3
) is used in air bags in automobiles. Write
a balanced chemical equation for the decomposition of
NaN
3
into N
2
(g) and Na(s). Calculate the volume in liters of
nitrogen gas generated at 21.0
o
C and 823 mm Hg by the
decomposition of 60.0 g of NaN
3
.
Strategy:
(1) Write balanced equation.
(2) Use stoichiometric coefficients to calculate moles of N
2
.
(3)Convert given parameters into appropriate units.
(4) Calculate V using the ideal gas law.
(1) 2 NaN
3
(s) 2 Na (s) + 3 N
2
(g)
mol NaN
3
= 60.0 g NaN
3
/ 65.02 g NaN
3
/ mol =
= 0.9228 mol NaN
3
mol N
2
= 0.9228 mol NaN
3
x 3 mol N
2
/2 mol NaN
3
= 1.38 mol N
2
T = 273.15 +21.0 = 294.2 K
P = 823 mm x 1 atm/760. mm = 1.08 atm
-1 -1
1.38 mol0.08206 L atm mol K 294.2 K
1.08 atm
nRT
V
P

= = = 30.8 L
EP102a: Calculate the density of ammonia gas
(NH
3
) in grams per liter at 752 mm Hg and
55.0
o
C.
Strategy:
(1) Assume one mole and calculate V for given
conditions.
(2) Use density = mass/volume to calculate density.
P = 752 mm Hg x (1 atm/ 760 mm Hg) =0.989 atm
T = 55.0
o
C + 273.15 = 328.2 K
-1 -1
1 mol0.08206 L atm mol K 328.2 K
0.989 atm

nRT
V
P
= =
= 27.2 L
17.03 g
27.2 L
mass
density
V
= = =
-1
0.626 g L
Calculation of Molar Mass
n = =
P x V
R x T
Mass
Molar Mass
Molar Mass = M =
Mass x R x T
P x V
m
RT
nRT mRT
M
V
P P MP
mRT RT
M
VP P

= = =
= =
EP103: A volatile liquid is placed in 590.0 ml flask and allowed to
boil until only vapor fills the flask at a temperature of 100.0
o
C and
736 mm Hg pressure. If the masses of the empty and gas filled flask were
148.375g and 149.457 g respectively, what is the molar mass of
the liquid?
Strategy:
Use the gas law to calculate the molar mass of the liquid.
Pressure = 736 mm Hg x 1atm/760 mm Hg = 0.968 atm
Mass of gas = 149.457g - 148.375g = 1.082 g
-1 -1
1.082 g 0.08206 L atm mol K 373K
0.968 atm 0.5900 L

mRT
M
PV
= =

=
-1
58.0 g mol
Gas Mixtures
Gas behavior depends on the number,
not the identity, of gas molecules.
The ideal gas equation applies to each
gas individually and to the mixture as
a whole.
All molecules in a sample of an ideal
gas behave exactly the same way.
Daltons Law of Partial Pressures - I
In a mixture of gases, each gas contributes to the
total pressure: the pressure it would exert if the gas
were present in the container by itself.
To obtain a total pressure, add all of the partial
pressures: P
total
= P
1
+P
2
+P
3
+P
N
Pressure exerted by an ideal gas mixture is determined
by the total number of moles:
P=(n
total
RT)/V
n
total
= sum of the amounts of each gas pressure
the partial pressure is the pressure of gas if it was present
by itself.
P
1
= (n
1
RT)/V P
2
= (n
2
RT)/V P
3
= (n
3
RT)/V
the total pressure is the sum of the partial pressures.
P= (n
1
RT)/V + (n
2
RT)/V + (n
3
RT)/V
= (n
1
+n
2
+ n
3
)(RT/V) =(n
total
RT)/V
Partial pressures in terms of mol fractions
1 1
1 1
1 2 3
P n
= P = x P
P n + n + n
EP104: Daltons Law of Partial Pressures
A 2.00 L flask contains 3.00 g of CO
2
and 0.100 g
of helium at a temperature of 17.0
o
C.
What are the partial pressures of each gas, and
the total pressure?
T = 17.0
o
C + 273.15 = 290.2 K
n
CO2
= 3.00 g CO
2
/ (44.01 g CO
2
/ mol CO
2
)
= 0.0682 mol CO
2
2
2
-1 -1
0.0682 mol 0.08206 L atm mol K 290.2 K
2.00 L
CO
CO
n RT
P
P
= =
= 0.812 atm
n
He
= 0.100 g He / (4.003 g He / mol He)
= 0.0250 mol He
P
Total
= P
CO2
+ P
He
= 0.812 atm + 0.298 atm
P
Total
= 1.110 atm
-1 -1
0.0250 mol 0.08206 L atm mol K 290.2 K
2.00 L
He
He
n RT
P
P
= =
= 0.297 atm
EP105: Daltons Law using mole fractions
A mixture of gases contains 4.46 mol Ne, 0.740
mol Ar and 2.15 mol Xe. What are the partial
pressures of the gases if the total pressure is
2.00 atm ?
Strategy:
(1) Calculate mol fraction each gas
(2) Partial pressure = mol fraction x total P
Total # moles = 4.46 + 0.74 + 2.15 = 7.35 mol
X
Ne
= 4.46 mol / 7.35 mol = 0.607
P
Ne
= X
Ne
P
Total
= 0.607 ( 2.00 atm) = 1.21 atm
X
Ar
= 0.740 mol / 7.35 mol = 0.101
P
Ar
= X
Ar
P
Total
= 0.101 (2.00 atm) = 0.202 atm
X
Xe
= 2.15 mol / 7.35 mol = 0.293
P
Xe
= X
Xe
P
Total
= 0.293 (2.00 atm) = 0.586 atm
Whats Behind the Ideal Gas Law?
A purely empirical law - solely the
consequence of experimental
observations
Explains the behavior of gases over a
limited range of conditions.
A macroscopic explanation. Says
nothing about the microscopic behavior
of the atoms or molecules that make up
the gas.
The Kinetic Theory of Gases
Starts with a set of assumptions about the
microscopic behavior of matter at the atomic level.
Supposes that the constituent particles (molecules)
of the gas obey the laws of classical physics.
Accounts for the random behavior of the particles
with statistics, thereby establishing a new branch
of physics - statistical mechanics.
Offers an explanation of the macroscopic behavior
of gases.
Predicts experimental phenomena that ideal gas
law cant predict. (Maxwell-Boltzmann Speed
Distribution)
The Four Postulates of the Kinetic Theory
A pure gas consists of a large number of
identical molecules separated by distances
that are great compared with their size.
The gas molecules are constantly moving in
random directions with a distribution of
speeds.
The molecules exert no forces on one
another between collisions, so between
collisions they move in straight lines with
constant velocities.
The collisions of molecules with the walls of
the container are elastic; no energy is lost
during a collision. Collisions with the wall of
the container are the cause of pressure.
An ideal gas
molecule in a cube
of sides L.
Cartesian Coordinate System for the Gas Particle
Cartesian Components of a
Particles Velocity
n. informatio l directiona
no conveys and quantity scalar a is that Note
axes. Cartesian
principal three the along velocity the of components
are and , and particle the of speed the is Where
2 2 2 2
u
u u u u
u u u u
z y x
z y x
+ + =
Consider the force exerted
on the wall by the
component of velocity
along the x axis.
Calculation of the Force Exerted on a
Container by Collision of a Single Particle
( )
( )
2
2
2 2
2
2
length of box

speed
2
2 and similarly for and
,
2
2 2 2
x x
x
x x
x x y z
y
x z
tot
mu
u
F ma m
t t
mu mu
L
t
u
u mu
F mu F F
L L
Thus
mu
mu mu m
F u
L L L L

= = =



=
= =

= =


= + + =
Calculation of the Pressure in Terms of
Microscopic Properties of the Gas Particles
2
,
2
Since the number of particles in a givengas sample can be expressed
average over
as , where is the number of moles and is Avogadro's
square of speed of all particles

!
num
tot one particle
A A
m
F u
L
nN n N
=
2
2 2
2 3
2
ber,
2
2 /
6 3
1
2
2
3
tot A
Tot
A A
Tot
A
m
F nN u
L
F mu L mu
P nN nN
Area L L
nN mu
P
V

=
= = = =






= =

2
A
mu
nN
3V
n Kinetic Energy/mole
2
3 V
The Kinetic Theory Relates the
Average Kinetic Energy of the
Particles to Temperature
from ideal gas law

Note that is independent of molecular mass
2
or

3
3


2
!

avg
avg
nKE
P
V
RT
PV
KE
n

=


= =
avg
avg
3
KE = RT
2
KE
Root Mean Square Speed and
Temperature
2
2
1 3
2 2
A
rms
N mu RT
u u

=


=
3RT
M
where R is the gas constant (8.314 J /mol K), T is the
temperature in kelvin, and Mis the molar mass expressed in
kg/mol (to make the speed come out in units of m/s).
2
,
2
independent of !
tot one particle
m
F u
L
m
=
Not all molecules have the same speed.
But what is the distribution of speeds in a
large number of molecules? The kinetic
theory predicts the distribution function
for the molecular speeds.
Molecular Speed Distribution
The Mathematical Description of the
Maxwell-Boltzmann Speed Distribution
2
2 2
-23
( ) 4
2
where: peed in , mass of particle in kg
Boltzman's constant = 1.38066 10 J /K,
and temperature in K

B
mu k T
B
B A
m
f u u e
k T
u s m s m
k R N
T

=


= =
= =
=
f(u)du is the fraction of molecules that have
speeds between u and u + u.
The distribution of
molecular speeds for N
2
at three temperatures
Features of the Speed Distribution
The most probable speed is at the peak of
the curve.
The most probable speed increases as the
temperature increases.
The distribution broadens as the
temperature increases.
Relationship between molar mass and
molecular speed at fixed T
The Speed Distribution Depends on
Molecular Mass
The most probable speed increases as the
molecular mass decreases.
The distribution broadens as the molecular
mass decreases.
Calculation of Molecular Speeds
and Kinetic Energies at 300.0 K
Molecule H
2
CH
4
CO
2

Molecular
Mass (g/mol)
2.016 16.04 44.01
Kinetic Energy
(J /molecule)
6.213 x 10
- 21
6.213 x 10
- 21
6.213 x 10
- 21

Speed
(m/s)

1,926 683.8 412.4

2
2
1 3
2 2
A
rms
N mu RT
u u

=


=
3RT
M
Various Ways to
designate
the average
Speed.
Molecular Mass and Molecular Speeds
Molecule H
2
CH
4
CO
2
Molecular
Mass (g/mol)
Kinetic Energy
(J /molecule)
rmsspeed
(m/s)
2.016 16.04 44.01
6.213 x 10
- 21
6.213 x 10
- 21
6.213 x 10
- 21
1,926 683.8 412.4
Larger
Same Kinetic Energy
Slower
The Three Measures of the Speed of a
Typical Particle
3
2
8
rms
mp
avg
RT
u
M
RT
u
M
RT
u u
M
=
=
= =
EP106: Calculate the Kinetic Energy of a
Hydrogen Molecule traveling at 1.57 x 10
3
m/sec.
Strategy: (1) calculate mass of molecule. (2) Use KE=1/2mu
2
Mass = 2.016 g/mol x 10
-3
kg/g
6.022 x 10
23
molecules / mol
= 3.348 x 10
- 27
kg / H
2
molecule
KE = 1/2 mu
2
= 1/2 (3.348 x 10
- 27
kg/ molecule)
x ( 1.57 x 10
3
m/sec)
2
KE = 4.13 x 10
- 21
kg m
2
/ sec
2
molecule
KE = 4.13 x 10
- 21
J / molecule
The Process of Effusion
Effusion
Effusion is the process whereby a gas escapes from its
container through a tiny hole into an evacuated space.
According to the kinetic theory a lighter gas effuses faster
because the most probable speed of its molecules is higher.
Therefore more molecules escape through the tiny hole in unit
time.
This is made quantitative in Graham's Law of effusion: The rate
of effusion of a gas is inversely proportional to the square root
of its molar mass.
1
Rateof effusion speed
M

Effusion Calculation
2
mass of He 4.003
1.409
mass of H 2.016
= =
EP107: Calculate the ratio of the effusion rates of helium
and hydrogen through a small hole.
Strategy:
(1)The effusion rate is inversely proportional to square root of
molecular mass.
(2) find the ratio of the molecular masses and take the square
root.
(3)The inverse of the ratio of the square roots is the effusion rate
ratio.
2
effusion rate He 1
0.7097
effusion rate H 1.409
= =
Path of one
particle in
diffusing
through the
gas.
Diffusion
The movement of one gas through another by
thermal random motion.
Diffusion is a very slow process in air
because the mean free path is very short (for
N
2
at STP it is 6.6x10
-8
m). Given the nitrogen
molecules high velocity, the collision
frequency is also very high
(7.7x10
9
collisions/s).
Diffusion also follows Graham's law:
M
1
diffusion of Rate
Diffusion of a
gas particle
through a
space filled
with other
particles
Relative Diffusion Rates of NH
3
and HCl
Relative Diffusion Rate of NH
3
compared to HCl in
the reaction
NH
3
(g) + HCl(g) = NH
4
Cl(s)
HCl = 36.46 g/mol NH
3
= 17.03 g/mol
Rate
NH3
= Rate
HCl
x ( 36.46 / 17.03 )
1/ 2
Rate
NH3
= 1.463 Rate
HCl
Gaseous Diffusion Separation of
Uranium 235 / 238
235
UF
6
vs
238
UF
6
Separation Factor = S =
after Two runs S = 1.0086
after approximately 2000 runs
235
UF
6
is > 99% Purity !
Y - 12 Plant at Oak Ridge National Lab
(238.05 + (6 x 19))
0.5
(235.04 + (6 x 19))
0.5
The ideal gas law is accurate over only a range
of conditions
The effect of intermolecular attractions on measured gas
pressure.
The effect of
molecular
volume on
measured gas
volume.
The van der Waals equation of state is valid over a
wider range of conditions than the ideal gas law:
( ) nRT nb V
V
a n
P =

+
2
2
Where P is the measured pressure, V is the
container volume, n is the number of moles of gas
and T is the temperature. a and b are the van der
Waals constants, specific for each gas.
EP109: van der Waals Calculation of a Real gas
Problem: A tank of 20.00 liters contains chlorine gas at a temperature
of 20.00
0
C at a pressure of 2.000 atm. The tank is pressurized to a new
volume of 1.000 L and a temperature of 150.00
0
C. Calculate the final
pressure using the ideal gas equation, and the Van der Waals equation.
-1 -1
2.000atm20.00L
1.663 mol
0.8206 L atm mol K 273.15 K
PV
n
RT
= = =
-1 -1
1.663 mol 0.08206 L atm mol K 423.15 K
57.75 atm
1.000L
ideal
nRT
P
V

= = =
( )
( )
2
2
-1 -1
-1
2
2 -2
2
1.663 mol 0.8206 L atm mol K 423.15 K
1.000L 1.663 mol 0.0562 mol L
1.663 mol 6.49atm L mol
63.7 19.9
1.00
45.8 a
0 L
tm
vdW
nRT n a
P
V nb V
=

= =
57.75 atm
ideal
P =
If attractive interactions dominate
ideal vdW
P P >
EP110: Gas Law Stoichiometry
Problem: A 2.79 L container of ammonia gas for which P= 0.776 atm
and T=18.7
o
C is connected to a 1.16 L container of HCl gas for which
P= 0.932 atmand T= 18.7
o
C. What mass of solid ammonium chloride
will be formed? What gas is left in the combined volume, and what
is its pressure?
Strategy:
1) Calculate the moles of each reactant and determine limiting reactant.
2) Calculate the mass of product from balanced equation
3) Determine which reactant is left and its pressure
Solution:
Balanced equation: NH
3
(g) + HCl (g) NH
4
Cl (s)
T
NH3
= 18.7
o
C + 273.15 = 291.9 K
3
-1 -1
0.776 atm 2.79 L
0.0903 mol
0.08206 L atm mol K 291.9 K
NH
PV
n
RT

= = =

-1 -1
0.932 atm 1.16 L
0.0451 mol
0.08206 L atm mol K 291.9 K


HCl
PV
n
RT

= = =

HCl is the limiting reactant

4
53.5 g
mass product 0.0451 mol 2.41 g NH Cl
mol
= =
3
NH remaining 0.0903 mol - 0.0451 mol 0.0452 mol
V= 1.16 L + 2.79 L = 3.95 L
= =
3
-1 -1
0.0452 mol 0.08206 L atm mol K 291.9 K
0.274 atm
3.95 L
NH
nRT
P
V

= = =
Energy used to create wealth and demand will grow
All aspect of economy depend on energy
U.S.A.
Canada
Taken from R. G. Watts, Engineering
Response to Global Climate Change, Lewis
Publishers, New York, 1997.
100
500
1000
5000
10,000
$ 20,000
50,000
$ 200
2000
0.01
0.10
1.0
10
100
POWER CONSUMPTION
M
e
a
n

G
r
o
s
s

D
o
m
e
s
t
i
c

P
r
o
d
u
c
t

(
$

p
e
r

P
e
r
s
o
n

p
e
r

Y
e
a
r
)
Bangladesh
China
Mexico
Poland
South Korea
(Former
U.S.S.R.)
France
Japan
U.K.
SLOPE = 23/kWhr
AFFLUENCE
POVERTY
kW/ person
Mean Global Energy
Consumption, 1998
4.52
2.7
2.96
0.286
1.21
0.286
0.828
0
1
2
3
4
5
TW
Oil Coal Biomass Nuclear Gas Hydro
Renew
Total: 12.8 TW U.S.: 3.3 TW (99 Quads)
80% from fossils fuels
2004: 80 millions barrels oil per day
The Trouble with Using
Hydrocarbons
All those carbon atoms react to form CO
2
molecules.
CO
2
is a greenhouse gas.
It traps infrared radiation in the
troposphere, heating lower atmosphere.
Earths Surface absorbs visible light.
emits thermal radiation in infrared.
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
CO
2
Combustion produces other
greenhouse gases
Combustion of petroleum produces CO, CO
2
, NO and
NO
2
together with unburned petroleum.
N
2
+ O
2
2 NO; 2 NO + O
2
2 NO
2
NO
2
NO + O (reactive) : O + O
2
O
3
(ozone)
This net production of ozone then produces other
pollutants.
World World Energy Energy
Millions of Barrels per Day (Oil Equivalent)
300
200
100
0
1860 1900 1940 1980 2020 2060 2100
Source: John F. Bookout (President of Shell USA) ,Two Centuries of Fossil Fuel Energy
International Geological Congress, Washington DC; July 10,1985.
Episodes, vol 12, 257-262 (1989).
1860 1900 1940 1980 2020 2060 2100
1860 1900 1940 1980 2020 2060 2100
0
5
10
15
20
25
30
35
40
45
50
O
i
l
C
o
a
l
G
a
s
F
i
s
s
i
o
n
B
i
o
m
a
s
s
H
y
d
r
o
e
l
e
c
t
r
i
c
S
o
l
a
r
,

w
i
n
d
,

g
e
o
t
h
e
r
m
a
l
0.5%
Source: BP & IEA
2004
0
5
10
15
20
25
30
35
40
45
50
O
i
l
C
o
a
l
G
a
s
F
u
s
i
o
n

/

F
i
s
s
i
o
n
B
i
o
m
a
s
s
H
y
d
r
o
e
l
e
c
t
r
i
c
S
o
l
a
r
,

w
i
n
d
,

g
e
o
t
h
e
r
m
a
l
2050
The ENERGY REVOLUTION
(The Terawatt Challenge 1TW = 10
12
W)
14.5 Terawatts
220 M BOE/day
30 -- 60 Terawatts
450 900 MBOE/day
The Basis of Prosperity
20
st
Century = OIL
21
st
Century = ??
Consequences of Increasing
World Energy Demand
Ten billion people consuming energy
as North Americans and Europeans do today
would raise world energy demand tenfold
6 billion tons of carbon released into
atmosphere per year today
More than 6 tons per capita in US
60 billion tons per year in 2100 ???
83 billion tons CO
2
per year in 2100 ???
Is Greenhouse Effect Bad?
Lets compare Mars, Earth, Venus.
A
l
t
i
t
u
d
e

(
k
m
)
50
100
Temperature (Kelvin)
100 400 800
A little greenhouse effect
is good. s show surface
temperature without the
greenhouse effect.
A lot of greenhouse effect is
very bad. Example: Venus.
Temperature over the last 420,000 years
Intergovernmental Panel on Climate Change
We are
here
CO
2
Unstable
Glaciers
Surface melt on
Greenland ice sheet
descending into
moulin, a vertical shaft
carrying the water to
base of ice sheet.
Source: Roger Braithwaite
If CO
2
can be captured from power plants , growth
in greenhouse gases can be avoided.
Buzzword: carbon sequestration
Current technologies use cryogenic capture or amine
absorbers. 10 times more expensive than acceptable
Natural capture by forests and oceans
Capture and injection into geological formations?
Capture and injection into deep oceans?
Mineralization; react with MgOto form MgCO
3
?
Microbial conversion into CH
4
and/or acetates?
Alternate Forms of Energy
Fossil fuels will be hard to replace.
Small volume large energy release.
Atomic nuclei? Most are very stable.
A few large ones can be induced to fission.
T
h
e
s
e

n
e
u
t
r
o
n
s

h
i
t

O
t
h
e
r

n
u
c
l
e
i

c
a
u
s
i
n
g

C
h
a
i
n

r
e
a
c
t
i
o
n
.
Nuclear Power
Excellent energy
output: 10
14
J /kg,
= 10,000 gallons of
gasoline.
Need good, solid
containment
vessels.
Final products
are still radioactive,
(alpha, beta decay).
Need long term
disposal solution.
95
Nuc l ear Reac t or s i n t he Wor l d
By the end of 2002:
30 countries
441 reactors
359 GWe
16% of electricity production
7% of primary energy
Source : AIEA Source : AIEA
Wind Power
Turbines can provide
~MWatt when running.
Wind farms can have up to
200 turbines.
over 500 gallons of gas/day.
Problem: calm.
Answer: storage.
fan
gearbox
dynamo
Electric Potential of Wind
http://www.nrel.gov/wind/potential.html
In 1999, U.S
consumed
3.45 trillion
kW-hr of
Electricity =
0.39 TW
Wave and Geothermal Power
Wave farms: Convert wave motion to circular drive
turbines: ~50 kWatts/m
At tectonic plate boundaries, geothermal plants can tap the heat
of the earths interior
Geothermal Energy
Potential
Renewable Energy Cost Trends
Levelized cents/kWh in constant $2000
1
Wind
1980 1990 2000 2010 2020
PV
C
O
E

c
e
n
t
s
/
k
W
h
1980 1990 2000 2010 2020
40
30
20
10
0
100
80
60
40
20
0
Biomass
Geothermal
Solar thermal
1980 1990 2000 2010 2020 1980 1990 2000 2010 2020 1980 1990 2000 2010 2020
C
O
E

c
e
n
t
s
/
k
W
h
10
8
6
4
2
0
70
60
50
40
30
20
10
0
15
12
9
6
3
0
Source: NREL Energy Analysis Office (www.nrel.gov/analysis/docs/cost_curves_2002.ppt)
1
These graphs are reflections of historical cost trends NOT precise annual historical data.
Updated: October 2002
25
35
45
55
1990 1995 2000 2005 2010 2015 2020 2025
Year
Space Heating
Space Cooling
Water Heating
Lighting
Refrigerators
PC
TV
Other
Business-As-Usual
Moderate Scenario
1990 Emissions Levels
1500
2100
2700
3300
A
25
35
45
55
1990 1995 2000 2005 2010 2015 2020 2025
Year
Space Heating
Space Cooling
Water Heating
Lighting
Refrigerators
PC
TV
Other
Business-As-Usual
Aggressive Scenario
1990 Emissions Levels
1500
2100
2700
3300
B
Source: Kammen & Ling, in press
Energy
Efficiency
Futures
Conclusions:
A) Moderate path:
1.5% annual
improvement
Emissions growth
halted at a savings
B) Aggressive
path:
2.9% annual
improvement
Meet Kyoto levels
by efficiency alone
& facilitate clean
energy market
development
Problem with Alternatives to
Hydrocarbons
Hydrocarbons:
1) store a lot of energy compactly.
2) are currently cheap.
Alternatives:
1) have large footprint.
2) may generate enough total energy, but at
low power rates.
3) solar and wind have low duty cycle.
165,000 TW
of sunlight
hit the earth
Solar Power
Suns main process: Turning H to He (fusion).
Suns output 4 x 10
26
Watts (or J oules/sec).
We see ~200 W/m
2
(in the US).
So at 15% efficiency, 1 m
2
, 10 hrs of sunlight 1 MJoule/day.
Problem:
Night, clouds.
Answer:
Storage.
(batteries, fuel cells).
6 Boxes at 3.3 TW Each = 20
6 Boxes at 3.3 TW Each = 20
TWe
TWe
From D. Kamen, UC Berkeley
Solar Land Area Requirements
3 TW
Solar Across Scales
MosconeCenter, SF: 675,000 W
Kenyan PV market:
Average system: 18W
US home: 2400 W
From D. Kamen, UC Berkeley
Learning Curve for PV Modules
(crystalline silicon)
2000
1980
1990
1
10
100
1 10 10
-1
10
-2
10
-3
10
-4
10
2
10
3
Cumulative installed PV Peak Power [GW
p
]
[/W
p
]
2020
2010
Today PV electricity costs about $0.20 - 0.25/kWh,
Which can be compared with $0.32/kWhPG&E charges for TOU
customers during peak time (noon-6pm)
From D. Kamen, UC Berkeley
E
f
f
i
c
i
e
n
c
y

(
%
)
Cu(In,Ga)Se
2
Amorphous Si:H
(stabilized)
CdTe
University
of Maine
Boeing
Boeing
Boeing
Boeing
ARCO
NREL
Boeing
Euro-
CIS
12
8
4
0
2000 1995 1990 1985 1980 1975
United Solar
16
20
24
28
32

Three-junction (2-terminal, monolithic)

Two-junction (2-terminal, monolithic)
NREL/
Spectrolab
NREL
NREL
Japan
Energy
Spire
North
Carolina
State University
Multijunction Concentrators
Thin Film Technologies
Best Research-Cell Efficiencies

Varian
RCA
Solarex
UNSW
UNSW
ARCO
UNSW
UNSW
UNSW
Spire
Stanford
Westing-
house
Crystalline Si Cells
Single Crystal
Multicrystalline
Thin Si
UNSW
Georgia Tech
Georgia Tech
Sharp
Solarex
Astro-
Power
NREL
AstroPower

Spectrolab
NREL

Emerging PV

Masushita
Monosolar
Kodak
Kodak
AMETEK
Photon
Energy
Univ.S.
Florida
NREL
NREL
NREL
Princeton
U. Konstanz
U.California
Berkeley
Organic Cells
NREL
NREL
Cu(In,Ga)Se
2
14x Concentration

Source: T. J . Berniard, NREL

From D. Kamen, UC Berkeley
Thin film-based PV modules could be printed on flexible
plastic backing using a printing press
Biodiesel Production
Biodiesel Production
100 lbs. of soybean oil
+
10 lbs. methanol
=
100 lbs. soy biodiesel
(B100)
+
10 lbs. of glycerin
~ 100,000 TW of energy is received
from the sun
Amount of land needed to capture 13 TW:
20% efficiency (photovoltaic) = 0.23%
1% efficiency (bio-mass) = 4.6%
Steven Chu Berkeley
> 1% conversion
efficiency may be
feasible.
Miscanthus yields: 30 dry tons/acre
100 gallons of ethanol / dry ton possible 3,000 gal/acre.
100 M out of 450 M acres ~300 B gal / year of ethanol
US consumption (2004) = 141 B gal of gasoline
~ 200 B gal of ethanol / year
US also consumes 63 B gal diesel
Steven Chu Berkeley
Sunlight
CO
2
, H
2
0,
Nutrients
Biomass
Chemical
energy
Self-fertilizing,
drought and pest
resistant
Improved
conversion of
cellulose into
chemical fuel
Cellulose 40-60% Percent Dry Weight
Hemicellulose 20-40%
Lignin 10-25%
The majority of a plant is structural material
Steven Chu Berkeley
Greenhouse Gases
-
25
50
75
100
125
-10 -8 -6 -4 -2 0 2 4 6 8 10 12 14 16 18 20 22 24
Net Energy (MJ / L)
N
e
t

G
H
G

(
g
C
O
2
e

/

M
J
-
e
t
h
a
n
o
l
)
Pimentel
Patzek
Shapouri
Wang
Graboski
Gasoline
de Oliviera
Today
CO
2
Intensive
Cellulosic
Original data
Commensurate values
Gasoline
EBAMM cases
Dan Kammen, et al. (2006)
40% of Oil used for Vehicles:
Do we need bigger SUVs..
The Kenworth Grand Dominator
- Extra high roof/cathedral ceilings
- Power expandable sides
- Full lavatory
The Peterbuilt Crusader
All Sport Denali
The worlds first two story high
performance sport brute
Crusader-E Edition: includes elevator
Source: http://poseur.4x4.org/futuresuv.html
From D. Kamen, UC Berkeley
or more fuel efficient cars?
Fuel Cell Detail
1. Hydrogen goes to Anode,
(can use hydrocarbon fuel)
Oxygen goes to Cathode.
2. Anode strips electrons from
hydrogen, H+ ions enter the
membrane
3. Since electrons cannot
enter the membrane they
go through the external circuit.
4. When electrons get back to the
Cathode, they combine with H+
and O to form water.
membrane
Office of Fossil Energy, U.S. Department of Energy
Office of Fossil Energy, U.S. Department of Energy
Fuel Cell Points
Each individual cell provides ~0.7 V.
Use many in astack.
Where do you get Hydrogen?
can use hydrocarbons,
wastewater digesters, landfills,
biomass.
can also run the fuel cell backward
(use solar, wind, etc. power to convert
water to H
2
and O
2
).
Greenhouse Comparison:
FCVs, ICEs and Hybrid Vehicles
Source: Bevilacqua-Knight, 2001
From D. Kamen, UC Berkeley
Generating H
2
by
splitting water using
visible light
From M. Graetzel, ETH Lausanne
Chemists vital to solution
Availability of fossil fuels has enabled mass of humanity
to move beyond subsistence living.
But we really need to figure out how to live without
them.
Carbon loading of the atmosphere is reaching alarming
levels.
Scientific consensus on global warming.
Clean alternatives like solar, wind, etc. have problems of
rate, efficiency. Need to solve them. Nuclear will play a
role.
Answers to Numerical Problems
EP100: 2.08 atm EP101: 10.5 atm
EP102 30.8 L EP102a: 0.626 g L
-1
EP103: 58.0 g mol
-1
EP104: CO2 0.812 atm He 0.298 atm total 1.110 atm
EP105: Ne 1.21 atm Ar 0.202 atm Xe0.586 atm
EP 106: 4.13 x 10
-21
J EP 107: 0.7097
EP 108: 1.463 EP109: ideal 57.75 atm vdW 45.75 atm
EP 110: 2.41 g NH
4
Cl PNH
3
= 0.274 atm