Part I Thermodynamics

Study of Transformations of Energy

Why do we need to know Thermodynamics?
Thermodynamics is central to chemistry,
biological processes, and thus central to life.
It explains why reactions occur (the driving forces of the
reactions), and the energy a reaction generates or requires.
1. Introduction: The Properties of Gases
! Gases form the working substance of many machines
(e.g., heat engines, refrigerators) and it is important to
understand their properties.
! The gas phase is also the simplest state of matter to
treat theoretically, and it shows limiting behavior that
is universal. This enables us to make a number of
useful generalizations.
! In the early stages of developing and understanding
thermodynamic concepts, we shall deal largely with
the gas phase because of its simplicity and generality.
heat engine: take thermal energy and convert it into mechanical energy
State, State Function, Equation of State
The state of a system is defined by a particular set of properties,
which are also referred to as state functions (e.g., p, V, T, and n).
Their values describe the state of a system and can be related by
an algebraic expression called an equation of state.
1.1 Ideal Gas Equation of State
~Ideal Gas Law
For ideal gases, and to a good approximation for any gas at a
|ow pressure, the state equation is:
nRT pV =
RT pVm =
or
fixing two state functions is enough to fix the other state functions as well.
reciprocal relationship
(i.e. P(V,T) and V(P,T) )
RT pV nRT pV
m
= = or
p: pressure
V: volume
V
m
= V/n: molar volume
n: number of moles
R: ideal gas constant
= 8.314 J K
1
mol
1
= 0.082 L atm K
1
mol
1
= 0.08314 L bar K
1
mol
1
= 8.314 L kPa K
1
mol
1
= 62.36 L Torr K
1
mol
1
Chemical Principles: The Quest for Insight
Peter Atkins, Loretta Jones, 2nd ed.
T: temperature
K = "C + 273.15
Torr = mmHg
pressure depends on the frequency of collisions and the amount of force per collision.
Torr = mmHg
Chemical Principles: The Quest for Insight
Peter Atkins, Loretta Jones, 2nd ed.
Procedures for using the ideal gas law:
To calculate a specific property (p, V, n, T) of a given gas.
Step 1. Rearrange pV = nRT to give the desired quantity on the
left, and all other quantities on the right.
Step 2. Convert Data to SI units. Note the T must be in Kelvins.
Step 3. Substitute data into the equation with
R = 8.314 J K
1
mol
1
.
Example:
a) To study weather phenomena one uses sensors carried by
balloons. Assume a radius of the balloon of r = 2.5 m. Calculate
the amount of Helium that is needed to fill the balloon to
1.01325 bar at 25 "C.
(Answer: n = 2675.35 mol)
RT
pV
n nRT pV = =
b) Response of a gas to a change in condition.
How does the volume of the balloon change when the
temperature increases by 5 "C?
(Answer: V
new
= 66.55 m
3
)
p
T nR
V T nR V p nRT pV
A
= A A = A =
Do you know the gases around us?
Troposphere: T decreases with increasing altitude.
Tropopause: From 11 to 16 km, constant T (55!C)
Stratosphere: From 16 to 45 km, T rises.
Due to Ozone formation, absorbs UV radiation
Stratopause: from 45 km up, T reaches 0!C.
Mesosphere: T drops again.
Mesopause: About 100!C
Thermosphere: T rises to over 1000!C at very high
altitude.
Chemical Principles: The Quest for Insight
Peter Atkins, Loretta Jones, 2nd ed.
1.2 The Kinetic Model of Gases,
Internal Energy and Temperature
The kinetic model of gases is a molecular interpretation of
the ideal gas law. It leads to a relation between internal
energy and temperature.
Assumptions (perfect gas):
1. A gas consists of molecules in random motion.
2. Gas molecules are infinitesimally small points.
3. The molecules move in straight lines until they collide.
4. The molecules do not interact, except during collisions.
All collisions are e|astic!
Ideal gas exerts pressure on the
walls of its container. Consider a
single molecule of mass m
contained in this box and moving
with velocity v.
Chemical Principles: The Quest for Insight
Peter Atkins, Loretta Jones, 2nd ed.
v
2
= v
x
2
+ v
y
2
+ v
z
2
t
t
mv
t
v
m ma F
A
A
=
= = =
momentum
Iorce

) (

distance
1
Irequency
distance
v
t
t v
=
A
=
A =
volume
distance Iorce
area
Iorce
pressure

= =
/
Simplified Derivation:
Box size: x = |, y = |, z = |, Box Volume:V = ||| = |
3
For the moment we focus attention on the x-direction
only. The momentum of the molecule in this
direction is mv
x
, which we take as positive if the
molecule is moving from left to right. When it strikes
the right-hand wall, it is reflected back elastically and
its momentum simply changes from +mv
x
to mv
x
, so
that the change in momentum is
Amomentum = 2mv
x
.
The molecule must travel a distance 2| (to the other side of the box and back) before it can
strike the right-hand wall again, so that the frequency with which it strikes the right wall is
1/At = v
x
/ (2|), and the rate of change of momentum at this wall (the force) is:
force = Amomentum / At = 2mv
x
v
x
/ (2|) = mv
x
2
/ |.
Hence the pressure of molecule i on the right wall is:
p
i
= force / area = (Amomentum / At) / area = (mv
x,i
2
/ |) / |
2
= mv
x,i
2
/ |
3
= mv
x,i
2
/ V.
If the box contains N identical molecules, the total pressure is:
2
1
2
,
1
2
,
1
1
x
N
i
i x
N
i
i x
N
i
i
v
V
Nm
v
N V
Nm
v
V
m
p p = = = =

= = =
mean square velocity in x
Recall: mass density = m / V
2 2

x x
v Nm pV v
V
Nm
p = =
Since all directions are equivalent:
(v
x
2
) = (v
y
2
) = (v
z
2
) = (v
2
) / 3.
|
|
.
|

\
| + + +
=
N
v v v
v
N
2 2
2
2
1 2
...
Mean square velocity:
Therefore, pV = Nm (v
2
) / 3
and hence for 1 mol, pV = N
A
m (v
2
) / 3 = RT ( N
A
m (v
2
) = 3RT )
(N
A
is Avogadro`s number = 6.022 10
23
mol
1
)
Thus the average translational kinetic energy of one mole of an ideal gas is:
E
trans
= N
A
(1/2) m(v
2
) = (3/2)RT,
(each of the 3 translational degrees of freedom contributes RT/2 to E
trans
)
or for one molecule,
e
trans
= (3/2)k
B
T, where k
B
= R/N
A
is Boltzmann`s constant.
It can be shown more generally:
The internal energy U of the ideal gas (pV = nRT) is a function of T only!
For Chem 205, U E.
Equipartition Principle (high-temperature limit)
As the previous argument has shown each of the 3
translational degrees of freedom contributes RT/2 to the
translational energy. For a perfect gas as defined
previously this is the only contribution to the internal
energy U. In the more general case of molecules with
internal structure, which can rotate and vibrate, the
Equipartition Principle states that each translational and
rotational degree of freedom contributes RT/2 and each
vibrational degree of freedom contributes RT to the
total internal energy.
Therefore, rigid diatomic molecules have U = (7/2)RT,
because there are 3 translational, one vibrational, and 2
rotational degrees of freedom.
BUT, at room temperature the high-temperature limit is
usually reached only for translation and rotation, but not
for vibration, i.e., the vibration is not excited. Thus, the
internal energy is U = (5/2)RT.
The internal energy U of an ideal gas depends on temperature
only: U = U(T)
In real gases, the finite size of the molecules and the
interactions between them lead to deviations from the ideal
gas law. Consequently, the internal energy is no longer a
function of temperature alone, e.g., U = U(T,V).
We need new Equations of State for Real Gases
1.3 Real Gas, Van der Waals Equation
1. Repulsive interaction (Size effect): The repulsive interaction between molecules
implies that they cannot come closer than a certain distance. The actual volume
in which the molecules can move is thus reduced compared with the volume of
the container V. Therefore, we replace V in the ideal gas law by (V nb), where
b is the volume/mole (molar volume) occupied by the gas itself.
2. Attractive forces: Pressure depends on both the frequency of collisions with
the container walls and on the force of each collision. Attractive forces reduce
both factors in proportion to the gas density n/V. The resulting change in the
pressure is proportional to (n/V)
2
. Thus attractive forces reduce the pressure
that the gas exerts, such that the observed pressure p will be less than the ideal
gas pressure p
ideal
by an amount an
2
/V
2
. Therefore, p
ideal
in the ideal gas law is
replaced by (p + an
2
/V
2
).
( ) nRT nb V
V
n
a p =
|
|
.
|

\
|
+
2
2
repulsion attraction
Van der waals equation
Volume occupied by particles
Real Gas, Virial Equation
Compressibility factor: z = pV / (nRT)
For an ideal gas: z = 1
Experimental observations:
( ) nRT nb V
V
n
a p =
|
|
.
|

\
|
+
2
2
T = constant
different T for a certain substance
ideal gas
General virial equation:
... 1
3
4
2
3 2
+ + + + = = p
RT
B
p
RT
B
p
RT
B
nRT
pV
z
p p p
ts coeIIicien Virial ,... , ,
2 2 2 p p p
B B B
At moderate pressures, one often observes a linear dependence
of z with pressure. This linear behavior can be described by the
first two terms in the general virial equation:
p
RT
B
nRT
pV
z
p
+ = =
2
1
2. Laws of Thermodynamics
Overview:
Study of transformation of energy (energy output of chemical
reactions, direction of reactions, equilibrium conditions).
The zeroth law states: If A and C are in thermal equilibrium
with B, then A is in thermal equilibrium with C. This means
that they are at the same temperature, and forms the basis for
temperature comparisons - leads to the absolute scale.
The first law is a formulation of the conservation of energy.
The second law tells us in which direction a process (chemical
reaction) proceeds spontaneously.
The third law defines the absolute entropy.
System: Part of the universe
that interests us.
Surroundings: The rest
Universe System + Surroundings
Boundary: Interface between the
system and the surroundings
Properties of a system:
State functions such as mass, number,
volume, temperature, pressure, etc.
Equation of state:
Set of state functions describing a system
related by an
expression,
e.g., pV = nRT
State functions; inherent properties of system
Open system: Can exchange both energy and
matter with its surroundings
Closed system: Can exchange energy but not
matter with its surroundings
Isolated system: Can exchange neither energy
nor matter with its surroundings
Isolated system has no
connection with the
surrounding.