Thermodynamics

Thermodynamic Systems, States and

Processes
Objectives are to:
define thermodynamics systems and states of systems
explain how processes affect such systems
apply the above thermodynamic terms and ideas to the laws of
thermodynamics
Classical means Equipartition Principle applies: each
molecule has average energy kT per in thermal equilibrium.
Internal Energy of a Classical ideal gas
At room temperature,
for most gases:
monatomic gas (He, Ne, Ar, )
3 translational modes (x, y, z)
kT E K
2
3
=
diatomic molecules (N
2
, O
2
, CO, )
3 translational modes (x, y, z)
+ 2 rotational modes (wx, wy)
kT E K
2
5
=
pV kT N U
2
3
2
3
= =

Internal Energy of a Gas
pV kT N U
2
3
2
3
= =
A pressurized gas bottle (V = 0.05 m
3
), contains
helium gas (an ideal monatomic gas) at a pressure p =
110
7
Pa and temperature T = 300 K. What is the
internal thermal energy of this gas?
( ) ( ) J 10 5 . 7 05 . 0 10 5 . 1
5 3 7
= = m Pa
Changing the Internal Energy
U is a state function --- depends uniquely on the state of the
system in terms of p, V, T etc.
(e.g. For a classical ideal gas, U =NkT )
WORK done by the system
on the environment
Thermal reservoir
HEAT is the transfer of thermal energy
into the system from the surroundings
There are two ways to change the internal energy of a system:
Work and Heat are process energies, not state functions.
W
by
= -W
on

Q
Work Done by An Expanding Gas
The expands slowly enough to
maintain thermodynamic equilibrium.
PAdy Fdy dW = =
Increase in volume, dV
PdV dW =
+dV Positive Work (Work is
done by the gas)
-dV Negative Work (Work is
done on the gas)
A Historical Convention
Energy leaves the system
and goes to the environment.
Energy enters the system
from the environment.
+dV Positive Work (Work is
done by the gas)
-dV Negative Work (Work is
done on the gas)
Total Work Done
PdV dW =
}
=
f
i
V
V
PdV W
To evaluate the integral, we must know
how the pressure depends (functionally)
on the volume.
Pressure as a Function of Volume
}
=
f
i
V
V
PdV W
Work is the area under
the curve of a PV-diagram.
Work depends on the path
taken in PV space.
The precise path serves to
describe the kind of
process that took place.
Different Thermodynamic Paths
The work done depends on the initial and final
states and the path taken between these states.
Work done by a Gas
Note that the amount of work needed to take the system from one
state to another is not unique! It depends on the path taken.
We generally assume quasi-static processes (slow
enough that p and T are well defined at all times):
This is just the area under the p-V curve
}
=
f
i
V
V
by
dV p W
V
p
p
V
p
V
dW
by
= F dx = pA dx = p (A dx)= p dV
Consider a piston with cross-sectional area A
filled with gas. For a small displacement dx,
the work done by the gas is:
dx
When a gas expands, it does work on its environment
What is Heat?
Q is not a state function --- the heat depends on the
process, not just on the initial and final states of the system
Sign of Q : Q > 0 system gains thermal energy
Q < 0 system loses thermal energy
Up to mid-1800s heat was considered a substance -- a
caloric fluid that could be stored in an object and
transferred between objects. After 1850, kinetic
theory.

A more recent and still common misconception is that
heat is the quantity of thermal energy in an object.

The term Heat (Q) is properly used to describe energy
in transit, thermal energy transferred into or out of a
system from a thermal reservoir

(like cash transfers into and out of your bank account)
Q U
An Extraordinary Fact
The work done depends on the initial and final
states and the path taken between these states.
BUT, the quantity Q - W does not depend
on the path taken; it depends only on the initial
and final states.
Only Q - W has this property. Q, W, Q + W,
Q - 2W, etc. do not.
So we give Q - W a name: the internal energy.
-- Heat and work are forms of energy transfer
and energy is conserved.
The First Law of Thermodynamics
(FLT)

AU = Q + W
on

work done
on the system
change in
total internal energy
heat added
to system
or
AU = Q - W
by

State Function Process Functions
1st Law of Thermodynamics
statement of energy conservation for a thermodynamic
system
internal energy U is a state variable
W, Q process dependent
system done work : positive
system added heat : positive
by
to
W
Q
W Q U = A
The First Law of Thermodynamics
by
dW dQ dE =
int
What this means: The internal energy of a system
tends to increase if energy is added via heat (Q)
and decrease via work (W) done by the system.
on
dW dQ dE + =
int
. . . and increase via work (W) done on the system.
on by
dW dW =
Isoprocesses
apply 1st law of thermodynamics to closed
system of an ideal gas
isoprocess is one in which one of the
thermodynamic (state) variables are kept
constant
use pV diagram to visualise process
Isobaric Process
process in which pressure is kept
constant
Isochoric Process
process in which volume is kept
constant
Isothermal Process
process in which temperature is held
constant
Isochoric (constant volume)
Thermodynamic processes of an ideal gas
( FLT: AU = Q - W
by
)
V
p
1
2
p V T Nk U A o = A o = A
0 pdV W
by }
= =
FLT:
U Q A =
Q
Temperature
changes
Isobaric (constant pressure)
V
p
1 2
V p T Nk U A o = A o = A
FLT:
( ) V p W U Q
by
A o A 1 + = + =
V p pdV W
by
A = =
}
Q
p
Temperature and
volume change
Isothermal (constant temperature)
}
= =
2
1
V
V
1
2
by
V
V
n NkT dV p W
0 = AU
FLT:
by
W Q =
p
V
1
2
( FLT: AU = Q - W
by
)
V
1
p
Q
Thermal Reservoir
T
Volume and
pressure change