THERMODYNAMIC RELATION

INTRODUCTION:
Eight properties of a system namely, temperature(T),
pressure(p), specific volume(v), internal energy(u), enthalpy(h),
Helmholtz function (F) and Gibbs function (G) have been
introduced in the previous chapters. In general, it is required to
find relation between the properties such as u, h, s, F and G which
cannot be directly measured and measureable quantities like p, v,
t. in this chapter , such relations are developed for system of
constant composition, which are subjected to non-flow or steady
flow processes. This chapter provides an interruption to the
mathematically intercalation of non-measurable and measurable
thermodynamics properties.
BASIC THERMODYNAMIC RELATIONS:
ISOLATED SYSTEM:
This is a system that does not exchange
energy with the surrounding media.
FIRST POSTULATE (equilibrium theorem):
Isolated system always reaches the
equilibrium state and never leaves it spontaneously.
SECOND POSTULATE (temperature):
Every equilibrium system is completely
determined by the set of external variables (volume, pressure,
magnetic field, etc.) plus one internal variable TEMPERATURE. At
least one additional internal parameter is needed to describe a
non-equilibrium system.
EQUILLIPRIUM PROCESSES:

This is a process that proceeds so slowly

that the system is always in equilibrium state
THE FIRST LAW OF THERMODYNAMICS:
The First Law of Thermodynamics is a
statement of conservation of energy in which the equivalence of
work and heat flow is taken into account.
dU=dQ+dW
The internal energy of the system U
depends only on the actual state of the system and not on the
way the system is driven to it, i.e. it is a function of state.
THE SECOND LAW OF THERMODYNAMICS:
Efficiency:
This is a measure of how well the heat flow from the hotter
thermal reservoir is converted to work. If the work done in one
complete cycle is W, then efficiency h is defined as the ratio of
the work done to the total heat flow Q

W
Q

One of the main consequences of the Second Law of

Thermodynamics is the existence of another function of state
called entropy
dS

dQ
T

Processes in closed systems are always connected with an

increase of entropy. In equilibrium the system has maximum of
entropy.

TdS dU dW
TdS dU pdV
dF SdT PdV

With the aid of these realation, the changes in these properties

can be computed.

USEFUL MATHAMATICAL EQUATION:

A brief summary of the types of partial differential
relations which are required to develope relationship between
measurable and nonmeasurable properties of ideal gases is given
below.
(A) Assume

Z=f(x, y)

then,

dZ=

dX +

. dY

..(8.1)
Z

where
is the rate of change of z with respective to
x, y is held constant, the equation(8.1) is said to be an exact
differential equation, since it involve es x, y and z which are
function of the second cross partials becomes a required condition
for exactness, if this principle is applied to equation (8.1).
Z
Z

Y X
X Y

As we know

2Z
2Z

YX XY

W= P.dv but w f (p.v)

But less assume that

W=f(p,v)

dW =

W
W

.dp
.dv
P v
V v

But
is zero because the work d equal to one at constant
volume is always zero.
W
.dv
V v

dW

This equation indicates that work done is

always to the work done at constant pressure and volume.