August 23, 2001

Reading: Chapter One.

Homework: None.

State of a system: The most important concept in thermodynamics is the state

of a system, which has to be uniquely defined by independent state variables. Any
system contains matter made up of particles (atoms, ions, and molecules). The
microscopic variables, such as masses, positions, and velocities of each and every
particle at any given time define the microscopic state of the system. Therefore, if
we know the microscopic state of a system, we can determine all of the properties
of the system. However, it is impossible to know such detailed information,
because there are ~1023 particles in constant motion. So, alternatively, in classical
thermodynamics, we determined the properties of a system by define the
macroscopic state of a system that is represented by the macroscopic variables,
temperature (T), pressure (P), and volume (V), which are experimentally
measurable.
Equation of State: For a simple one-component system with a single phase, the
state of a system can be uniquely defined by choosing any two independent
variables. If the chosen two variables are fixed, then the state of the system is
fixed, and hence all the other variables (properties) must have unique values
corresponding to this state. Therefore, there must be a unique relationship
between the different variables, which are called equation of state:
V=V(T,P), or P=P(V,T), or T=T(P,V).
State function: The equation of state defines the relationship between variables
that are state functions; they depend on only the state values of parameters but not
on the history of how the state was reached, i.e., they are path-independent.
Consider a process to move a system from state 1 with volume V1(T1,P1) to state 2
with V2(T2,P2). The state of the system is represented by two independent
variables T and p, and this process can proceed along an infinite number of paths,
with different ways of varying T and P. However, the change of volume is always
V=V2-V1. So, the change of volume depends only on the volume at state 1 and
the volume at state 2, independent of path, because V=(T,P) is a state function.
The differential of a sate function, representing an infinitesimal change of the
system is an exact differential, because state function is path independent. So,
V
V
dV =
dP +
dT
P T
T P
is an exact differential.

There can be many other state functions. One such example is the internal energy,
U. Since by defining any two variables of the system, e.g., V and T, the state of
the system is defined, so also are all other state functions. Therefore, the internal
energy can be given by U=U(V,T), or alternatively, U=(P,T) or U=U(P,V).
Similarly the differential of internal energy is exact:
U
U
dU =
dV +
dT .
V T
T V
Process function: Process functions are those that do depend on the path chosen.
These have to do with the interaction of the system with the surroundings. The
two most important process functions are heat and work: heat adsorbed (or
released) by the system and work done by (or on) the system, from the
surroundings.

(P2,V2)
P

Path 1
Path 2

(P1,V1)
V

Consider a system goes from (P1,V1,T1) to

(P2,V2,T2). There are no unique values of heat
(q) and work (w) associated with the change
of the system. The figure on left demonstrates
the case for work (w):
w=

P2 ,V2

PdV =

area under the P-V curve, is

P1 ,V1

clearly dependent on the path chosen. So, the

work is a process function.

The differential of a process function is NOT an exact differential, because the

process function is path dependent, so it cant uniquely represent the infinitesimal
change of the system. We use w and q (istead of dw and dq) to express the
differential of w and q; they are known as Pfaffian differentials. In other words, if
we choose two independent variables to represent the state of a system, a state
function is a unique function of these two variables, while a process function is
not. Therefore, the differential of a state function with respect to these two
variables is exact, while the differential of a process function with respect to these
two variables is NOT but a Pfaffian differential:

but

P = P(V,T),
V = V(P,T),
U = U(V,T),
w w(V,P),
q q(V,T),

dP is an exact differential;
dV is an exact differential;
dU is an exact differential;
w is a Pfaffian differential;
q is a Pfaffian differential.

Extensive vs. Intensive properties:

An extensive property depends on the size of the system, such as volume.
An intensive property is independent of the size of the system, such as
temperature and pressure.

Types of sytems:
(1)

Isolated: does not exchange heat, work, and matter with the
surroundings.
Closed: does not exchange matter with the surroundings.
Closed-Adiabatic: doest not exchange matter and heat with the
surroundings.
Closed-Rigid: doest note exchange matter and work with the
surroundings.
Open: exchange matter, heat, and work with the surroundings.

(2)
(3)
(4)
(5)

Absolute zero temperature:

Consider an one-component system,
V = V ( P, T )
V
V
dV =
dP +
dT
P T
T P
dV 1 V
1 V
=
dP +
dT
V
V P T
V T P
dV
= dP + dT
V
1 V

------ Isobaric expansivity;

V T P
1 V
=
------ Isothermal compressibility.
V P T

where, =

In 1802 GayLussac observed that the thermal expansion coefficient, for gas is a
constant. So,

1
V0

V
o

, where V0 is the volume at T = 0 C and P is kept constant.

T P

V
Thus, V ( P, T ) = V0 +
(T 0) = V0 + V0T .
T P
He obtained a value of 1/267 for . This was later refined by Regnalt in 1847 to
be 1/273. (For idea gas, =1/273.15.)

So, V ( P, T ) = V0 +

V0
T . Note V0 is a function of P.
273.15

The lowest value of V(P,T) is zero. Consequently, the lowest possible temperature
is T=-273.15oC, i.e., the absolute zero (0 K).

Idea gas:
A hypothetical gas that obeys Boyless and Charles laws exactly at all
temperatures and pressures is called ideal gas. Usually, gases at very low
pressures can be modeled as an idea gas.
Boyles law:

P0V (T , P0 ) = PV (T , P) ;

Charles law:

V ( P0 , T0 ) V ( P0 , T )
=
;
T0
T

Idea gas law:

PV P0V0
=
= const.
T
T0

Where P0 = standard pressure (1 atm)

T0 = standard temperature (absolute scale with 0oC=-273.15 K)
V0 = V(P0,T0) = 22.414 liters
Then, PV = RT,
R=

P0V0
= 0.082057 liter atm/degreee mole = 8.3144 joules/degree mole.
T0