1.

INTRODUCTION AND DEFINITIONS

1.1. Introduction

Thermodynamics is the science that deals with energy

transformations and the interactions between energy and
matter.
Current passing through a resistor, combustion, refrigeration, metal extraction, etc.
could be typical examples where energy transformations and/or interactions between
energy and matter take place.
Special emphasizes are given to those transformations that
involve heat (thermo) and mechanical work (dynamics), and
often situations where chemical considerations are involved.
Like all sciences, the basis of thermodynamics is experimental
observation. In thermodynamics these findings have been
formalized into certain basic laws. These laws are principles
drawn from experiments.
The problems that fall into the scope of thermodynamics can
be considered in two groups.
The first group of problems is related to computations of
energy differences between two physical conditions.
Heat released as a result of combustion of coke with air and the work required to
compress a gas could be examined in this group.
The second group of problems is related to determinations of
spontaneous directions of processes.
For example, thermodynamic computations can be used to decide whether water will
evaporate or not at 95oC when pressure is 0.8 atmosphere.
It should be noted that, thermodynamics could only determine whether
a specific process will take place or not. It does not give information
towards the rate of a possible process and/or microscopic mechanisms
involved in a transformation.

1.2. Basic Definitions

A thermodynamic system is defined as part of the universe
conceptually separated from the rest.
This serves a simplification in computations by focusing the attention to a small part of
the universe.
Everything that remains outside what has arbitrarily been
chosen as the system is called the surroundings.
The system is separated from the surroundings by the system
boundaries.
The system boundaries could be deformable, rigid, diathermal or adiabatic (or their
combinations).
A deformable boundary could allow the system or the
surroundings to perform mechanical work on each other.
No mechanical work can be performed when the boundary is
rigid.
A diathermal boundary could allow heat energy exchange, but
an adiabatic boundary does not permit heat energy exchange
between the system and the surroundings.
A system could be open, closed or isolated depending on the type of boundaries used.
An isolated system is one that is not influenced in any way by
the surroundings.
This means that no heat, work or mass exchange with the surroundings.
A Closed system (fixed mass) can exchange energy with the
surroundings but not mass.
Open system (involving flow of mass) exchanges both mass
and energy with the surroundings.

1.3. The Concept of State and the Equation of State

If it were possible to know the masses, positions, and all
modes of motion of all the constituent particles in a system,
than this mass of knowledge would serve to describe
microscopic state of the system.
Thus, to completely describe the behavior of a system from microscopic point of view,
it would be necessary to deal with an enormous number of equations. Even with a
large digital computer, this is a quite hopeless computational task. However, there are
two approaches to this problem that reduce the number of equations and variables to a
few that can be handled relatively easily in performing computations.
These are statistical and macroscopic state approaches.
In statistical approach "average" values are determined for
particles in the system on the basis of statistical considerations
and probability theory.
This is usually done in connection with an atom or group of atoms under
consideration. This is the approach used in the discipline of statistical mechanics.

Macroscopic state approach is used in classical

thermodynamics.
As the word macroscopic implies, it is concerned with the gross effects of many
molecules.
The state of the system can be defined as the physical
condition of the system as specified by a small set of
measurable variables (state variables).
The variables (properties) that depend on the quantity of the
system are extensive and those independent of the quantity are
called intensive. The ratio of an extensive variable to the mass
of the system is called specific property.
Specific properties resemble intensive properties -they are mass independent. But they
could be distinguished from intensive properties from their units (per unit mass). It
should be noted that terms variable, property and quantity are used alternatively.

Various state properties are related to each other.

In fact, for a closed system, containing a pure substance which does not undergo a
chemical change, experiments show that only any two of the properties of the system
need to be specified in order to define completely the state of the system. The values
of the remaining properties are specified by the nature of the substance
(automatically).
In the case of a simple system any two properties could be chosen as the independent
variables, and the choice is purely a matter of convenience.
The relationship between any property of a system and two
independent variables is called equation of state (for a simple
system).
For example, when pressure P and temperature T are taken as independent variables,
the volume of the system can be written as

V = V(T,P)

The relationship between V, T and P is the equation of state.

For a simple system any two intensive properties, like I1 and
I2 will give the values of all others. Thus

Ij = f(I1,I2) j = 3, 4, .. n

Extensive properties of a system can also be related to any two

of its intensive properties and the total mass, m.
Ej = m.f(I1,I2)

1.3.1. The Equation of State of an Ideal Gas

From the experimental observations of gases by Boyle (in
1660) at constant temperature, an inverse proportionality was found
between the pressure and volume of a gas.
A direct variation between volume and temperature was found for gases
under constant pressure by Charles (in 1787).
Later, Gay-Lussac (in 1802) observed a constant thermal expansion coefficient of
1/267 for gases under constant pressure.
More refined experiments by Regnault (in 1847) showed (thermal expansion
coefficient) to be 1/273.
Boyle's and Charles' findings for the behavior of different
gases varied slightly from one gas to another and generally,
gases with lower boiling points obeyed the laws more closely.
It was also found that above findings were valid for all gases
at low pressures.
It was found convenient to invent a hypothetical gas which obeys
Boyle's and Charles' laws at all values of temperature and pressure. This hypothetical
gas is termed the ideal gas, and for this gas α is 1/273.16.

The existence of a finite thermal expansion coefficient sets a limit on the thermal
contraction of the ideal gas; i.e. the volume of the gas is zero at -273.16oC. This limit
of temperature decrease -273.16oC, is thus the absolute zero of temperature. This
defines an absolute scale of temperature called the ideal gas temperature
scale, which is related to the centigrade scale by the equation

T(degrees absolute) = T(degrees centigrade) + 273.16

Application of Boyle's law to a gas initially at To temperature and Po pressure gives

Po V(To,Po) = P V(To,P) (1)

Application of Charles' law to this gas yields

V(To,P) V(T,P)
----------- = --------- (2)
To T

Combination of these two laws, by multiplying equations (1) and (2) gives

Po V(To,Po) V(To,P) P V(To,P) V(T,P)

---------------------------- = ------------------------ (3)
To T
Reorganization, by replacing To = 0oC and Po = 1 atmosphere and by setting
V(To,Po) = Vo and V(T,P) = V yields

Po Vo PV
--------- = ----- (4)
To T

From Avagadro's assumption Vo = 22.414 lt/mole, equation (4) for one mole becomes

PV
----- = R = 0.082057 lt.atm.mol-1K-1 (5)
T

where R is known as the gas constant. Equation (5) is called the ideal gas law or the
equation of state of an ideal gas.

At normal temperatures (not very low) and pressures (not very high) majority of gases
obey this law.

1.3.2. Generalized P-T-V Relationship

For any material, condensed or gases at high pressures, P-V-T are related in a
complicated way, since atoms or molecules interact.

V = V(T,P) per mole

dV = (∂V/∂T)P dT + (∂V/∂P)T dP (6)

define α = 1/V (∂V/∂T)P isobaric expansion coefficient

β = - 1/V(∂V/∂P)T isothermal compressibility

Therefore,

dV = α VdT - β VdP

divide by V

d ln V = α dT - β dP
when α and β are constants and defined with respect to a reference state To
temperature and Po pressure

V - Vo = α Vo(T - To) - β Vo(P - Po)

α and β are tabulated for various pressures and temperatures for many materials.

1.4. Thermodynamic Equilibrium

A system is in equilibrium (at rest) when its observable
properties do not change with time so long as the external
conditions are unaltered. This requires the system to be at thermal,
mechanical and chemical equilibrium at the same time.

For thermal equilibrium temperature, mechanical equilibrium pressure of the system

should not change with time. Chemical equilibrium requires the forward and backward
rates of chemical reactions involved to be the same.

1.5. Process and Path

Whenever one or more of the properties of a system is changed, a change in the state
of the system occurs. The
transition of a system from one state
(initial) to another (final) is called the process. In the course of
a process, system passes through a series of equilibrium states,
the locus of all these states form the path of the process.
Depending on the variable kept constant during a process, different names are given to
processes. The process is called isothermal when temperature is kept constant,
isobaric when pressure is kept constant and isochovic when volume is kept constant
during the process. Above terminologies could also be used to identify paths.