CHAPTER I

Fundamental Principles, Concepts & Definitions

OBJECTIVES: At the end of this chapter, the students will be able to:
 define thermodynamics;
 recall the applicable standard units;
 define the basic quantities and variables used, such as:
- mass
- weight acceleration
- force
- volume and density;
 describe the properties used to specify the state or condition of a substance
and the units in which the property is measured and its corresponding symbol
for:
-pressure
- temperature
- energy;
 give the distinction between:
-absolute and specific quantities
-intensive and extensive values;
 distinguish the three phases of substance (solid, liquid, gaseous);
 identify the factors which influence phase changes; and
 explain how fluids can have a liquid or a gaseous form.
THERMODYNAMICS DEFINED
Thermodynamics deals with the study of the quantitative relationship between heat
and other forms of energy, the processes involved in their transformation from one
form to another and their transfer from system to another.
RELATED QUANTITIES AND STANDARD UNITS
The internationally accepted system of measurement, the SI (International System)
units, is to be used throughout the discussion of various topics.
MASS
Mass is the quantity or amount of matter concentrated in a single body. It can be
expressed in terms of Metric (SI) Units – kilogram (kg) and gram (g).
1 kg=1000 g ; 1 g=1/1000 kg
1 milligram(mg)=1 /1000 g; 1 g=1000 mg
ACCELERATION
The acceleration of a moving body is always associated with change in velocity. This
change requires a certain amount of time. Thus, average acceleration is the ratio of
the change in velocity to the time required for that change to effect.
FORCE
Force can be defined simply as the result of a push or pull of one object to another. It
has a tendency to produce or prevent motion.
Force is expressed in terms of newton (N) , which is a force that will cause a mass of
1 kg to an acceleration of 1 m/s 2. Verifying from Newton's 2nd Law of Motion:
WEIGHT
Weight is defined as the gravitational force exerted towards an object due to its
attraction with other mass. If Force is related to the object's mass, then weight (W) of
the object on the surface of the earth is related to its mass.
Thus: Force = Weight. For objects, moving vertically as in free-falling bodies
(disregarding air resistance) the force that causes its acceleration is its weight. This
acceleration is better known as acceleration due to gravity (ag) that has a magnitude
of 9.81 m/s 2.

Therefore: From F=ma: Substituting a g to a, we get W=ma g

VOLUME & DENSITY
Density (ρ) is the ratio of the mass (m) of a substance to its volume (V)
m
It is denoted by: ρ=
V
Where:
ρ=density
m=mass
V =volume
The unit of density depends on the desired unit of mass and volume.
Densities of solids and liquids are almost constant under ordinary conditions
because they are only slightly compressible even when subjected to great amount of
stresses. For gases that are highly compressible, there is a need to specify the
condition to which they are subjected as basis for measuring its density since the
volume is greatly affected by factors such as temperature and pressure.
PRESSURE
The concept of pressure is useful in dealing with properties of liquids and gases.
Liquids need external support to maintain shape. The absence of which will mean
spreading of particles throughout. It follows that liquids exert force towards the walls
of the container resulting to pressure.
Likely. gases have no definite shape and volume. Its particles are constantly moving
at random as stated in the Kinetic Molecular Theory of Gases. This random motion
leads to collision between particles which bounce to the walls of the container
resulting to the increase in pressure.
Pressure is defined as the force (F) exerted per unit area (A).
F
P=
A
It may also be expressed in atmosphere (atm) which represents a pressure equal to
that exerted by air under standard condition (temperature = 273°K or 0°C).

Note: The unit psi Torr are included in the discussion for the simple reason that some
pressure gauges found in some ships are still calibrated using units in the English
system.
DEVICES USED FOR MEASURING PRESSURE
Most gauges record the difference between fluid pressure and local atmospheric
pressure. The standard atmospheric pressure is 760 mm Hg or 29.92 in. Hg at 0°C
or 14.696 psi or 1 atmosphere (atm).
1. U - tube manometer is used for measuring small pressure differences. It consists
of U - shaped tube with one end connected to the container and the other open to
the atmosphere and partially filled with liquid such as oil, water, mercury, or alcohol.
The difference in the surface level of the liquid indicates the pressure difference from
the local atmospheric condition. The equation is: P=P a+ ρ ag h
where:
P = absolute pressure
Pa= atmospheric pressure
ρ = density of the liquid
h = difference in the height of liquids in the two legs of the U - tube
a g=acceleration due to gravity (related to the weight or downward force exerted to
the liquid)

The absolute pressure P a depth h below the surface of the liquid open to the
atmosphere is greater than the atmospheric pressure by an amount ρ a g h
2. Barometer is used for measuring atmospheric pressure.
Some Common Types of Barometers:
a) Water Barometer is not convenient to use because of its large size.
b) Mercury Barometer consists of a glass tube 840 mm high, closed at the upper
end and open at the lower. A variation in atmospheric pressure causes the mercury
level to rise or fall by small amounts, rarely below 737 mm or above 775 mm at sea
level. The reading of the mercury barometer is reliable to within 0.1 mm.
c) Aneroid Barometer is one that is almost as accurate as the mercury barometer,
in which the atmospheric pressure bends the elastic top of a partially evacuated
drum. actuating a pointer. A suitable aneroid barometer is often used as altimeter
(instrument for measuring altitude), because pressure decreases rapidly with
increasing altitude (about 25 mm of mercury per 305 m at low altitudes).

3. Bourdon Gauge is used for higher pressure differences. This consists of a hollow
metal tube with an oval cross section, bent in the shape of a hook. One end is
closed, the other open and connected to the measurement region. If pressure (above
local atmospheric pressure) is applied, the oval cross-section will become circular
and at the same time the tube will straighten out slightly. Gauges used for rapidly
fluctuating pressures commonly employ piezoelectric or electrostatic sensing
elements that can provide an instantaneous response.

A negative gauge pressure reading indicates partial vacuum.

4. McLeod Gauge is used to measure low gas pressure (down to about 10" mm
mercury absolute), in which a measure volume of a gas at the unknown low pressure
is compressed at constant temperature to a much smaller volume, and then the
pressure is measured directly with a manometer. Various gauges are used for still
lower pressures, depending on radiation, ionization, or molecular effects.
ILLUSTRATIVE PROBLEM 3:
ILLUSTRATIVE PROBLEM 3:
TEMPERATURE
Temperature is defined as the degree of hotness or coldness of a substance. It
should not be confused with heat because heat is the transfer of energy from one
part of a substance to another caused by a difference in temperature. It can also be
described as that property which determines the direction of flow of heat between it
and its surroundings. Temperature is dependent upon the average kinetic energy of
molecules of substance.
Variation in temperature may result to expansion and contraction of substances.
change in resistance and exert varied pressure. Theoretically, molecules of a
substance would not show any activity when the temperature is at absolute zero,
which is the lowest temperature attainable by any substance.
The common temperature scales are:
1. Celsius Scale formerly known as Centigrade scale with a freezing point of 0°C
and a boiling point of 100°C for pure water.
2. Kelvin Scale or Absolute Scale, the unit of absolute temperature in the SI
system is the Kelvin. Zero is defined as the absolute zero of temperature -273.15°C.
All formulas in thermodynamics use absolute temperature; hence, conversion from
Celsius is essential.
3. Rankine Scale (very seldom used at present) also employs absolute zero as its
lowest point. The freezing point of water in this scale is 492°R and the boiling point is
672°R.
DEVICES FOR MEASURING TEMPERATURE
Ordinarily, temperature is measured by a thermometer, which comes in various
kinds depending upon the particular thermometric substance and its particular
thermometric property (a property that varies particularly with an increase and
decrease in temperature). The mercury thermometer has a temperature range of
−38 ° C ¿ 350° C . Alcohol in glass thermometer indicates the temperature by the
length of alcohol column ranging from 80 ° C to 100 ° C .
A gas thermometer makes use of a confined gas at constant volume as the
thermometric property. This is also known as the ideal gas temperature. The
approximate range is −269 ° C to 1600 °C . In 1933, scientists of 31 nations adopted a
new International Practical Temperature Scales (IPTS) with additional fixed
temperature points based on the Kelvin scale and thermodynamic principles. Among
them are the following:
1. Resistance thermometer - makes use of the electrical resistance of platinum
wire as the standard for temperature between - 190 °C and 660°C.
2. Thermocouple - a device, which measures temperature by the amount of voltage
or electromotive force (Emt) produced between two wires of different metals. It is
used for measuring temperature above 660°C to the melting point of gold, 1,063°C.
For temperature beyond 1,063°C, an optical pyrometer is used. It makes use of the
intensity of light of a wavelength emitted by a hot body. In 1954, by the international
agreement, the triple point of water was adopted as 273.16°K. This is the point at
which the three phases of water (vapor, liquid, and ice) are in equilibrium.
3. Cryogenics - the study and use of materials at very low temperatures (below
- 150°C; 123° above absolute zero on the Kelvin scale). Cryogenic temperatures are
achieved either by the rapid evaporation of volatile liquids or by the expansion of
gases (confined initially at pressures of 150 to 200 atmospheres) through a valve to
a region of lower pressure, or it may occur in the cylinder of a reciprocating engine,
with the gas driving the piston of the engine. This method is more efficient but more
difficult to apply.
COMPARISON OF VARIOUS TEMPERATURE SCALES
EQUATIONS FOR TEMPERATURE CONVERSIONS
Illustrative Problem 5
Illustrative Problem 6
ENERGY
Energy is the property of a body or a system of bodies by virtue of which work can
be performed on a result of its motion or its position in relation to forces acting on it.
Units of energy= units of work
System Work =Force × displacement Symbols
mks Joules ( J )=Newton× meter (N ∙ m)
cgs erg=dyne × centimeter (dyn ∙ cm)

Energy exists in various forms depending on the means it is generated. It may be by

chemical, mechanical, thermal, electrical, radiant, atomic, or nuclear. Mechanical and
thermal energy will be dealt with in details in the succeeding chapters.
PHASES OF SUBSTANCES
1. Solid is characterized by resistance to change in shape due to the strong
attraction between particles that are compact and arranged in definite patterns.
2. Liquid does not resist to change in shape because there are spaces between
particles which allow greater freedom of movement. The volume of liquid remains
unchanged because it has sufficient molecular attraction to resist the forces which
tend to alter their volume.
3. Gaseous substances have no resistance to change in shape due to the absence
of attraction between particles that are widely dispersed in a highly disordered
fashion. It has little resistance to change in its volume which is greatly affected by
temperature and pressure change. Gaseous substance has low density that result to
diffusion of particles if not confined in a container.
PHASE CHANGE
Phase change or change of state is change in the form or shape of a substance
brought about by loss of attractive force between molecules due to increase in their
kinetic energy caused by the application of heat. Most substances are solid at low
temperatures, liquids at medium temperatures, and gaseous at high temperatures,
but states are not always distinct. Change of substance from solid to liquid phase is
known as melting or fusion, and the temperature, which facilitates the change is its
melting point. The temperature at which liquid change to gas is boiling point, and
the process is called boiling. If vapor escapes not only from the surface but also
from within the liquid. When the formation of vapor takes place from the free surface
of the liquid, it is called evaporation. The range of melting and boiling points varies
widely. Helium remains a gas down to -269°C, and Tungsten remains solid up to
about 3,370°C. When vapor returns to liquid, the process is called condensation.
Some substances change from solid directly to gaseous or vapor state without
passing through the liquid state, this process is known as sublimation. Examples are
dry ice and naphthalene balls. The change of liquid to solid phase at very low
temperature is called freezing, and the temperature is called freezing point.
Phase Rule was formulated by J. Willard Gibbs, an American physicist as part of his
study of Thermodynamics. It describes the behavior of chemical systems in
equilibrium. An example of a chemical system is salt solution in which the
components are salt and water. Components of a chemical system can exist as gas,
liquid, or solid phases. The Phase Rule applicable only to heterogeneous systems
where two or more physically distinct phases are in equilibrium. A system can only
contain one gas phase but can contain any number of liquid and solid phases. For
example, an alloy of copper and nickel contains two solid phases: a mixture of
carbon tetrachloride and water contains two liquid phases. A salt solution contains
three phases: salt, the solid phase; water, the liquid phase; and water vapor formed
by evaporation is the gas phase.
Water is a heterogeneous chemical system of one component. The liquid and gas
phases, water and water vapor coexist over a wide range of temperatures and
pressures. At triple point, all these phases: water (liquid), water vapor (gas), and ice
(solid) coexist in equilibrium.
The Phase Rule is expressed in the equation:
F=C−P+2
Where:
F = is the number of variables (temperature, pressure, & concentration) that can be
changed without causing the disappearance of a phase or the emergence of a new
one.
C = is the number of chemical components of a system
P= is the number of phases present
It is applied in the solving of many practical problems, particularly in the field of
metal-alloy preparation and in chemical engineering and is also useful to geologists.
PHASE TRANSITION AND GASES
Under low temperature and high pressures or reduced volumes, the molecules in a
gas come under the influence of one another's attractive force. Under certain critical
condition, the entire system enters a high-density bound state and acquires a
bounding surface that signifies the onset of the liquid state. This process is called
phase transition.
Heat of fusion of a solid is the energy required to melt a unit mass of solid. For
example, the heat of fusion of ice is 80 cal /g at 0 ° C .
Heat of Vaporization is the amount of heat needed per unit mass of the substance
to transform to liquid to vapor at a particular temperature. Water for instance, needs
540 cal/ g at STP (T =0 ° C , P=76 cm Hg) to vaporize.