Thermodynamics:

Thermodynamics is the science of thermal energy of matter or a system of matters.

Thermodynamics is the study of the laws that govern the conversion of energy from one
form to another.

To have a better understanding of thermodynamics, we must have a fair idea that what
“energy” is.

Energy:
Energy is the capacity to do work or ability to cause changes. One of its most fundamental
laws is the “Conservation of Energy”, i.e., energy cannot be created nor destroyed
however during an interaction, energy may transform form from one form to other. .

Energy can exist in different forms. The subject thermodynamics divides a distinct
boundary like “Macroscopic” and “Microscopic” forms of energies. The macroscopic
energies are considered which are as a whole (like kinetic and potential energies) with
respect to some out side reference frame. The microscopic energies include energies due to
intermolecular structure and are independent to the out side reference frame.

Thermal and Mechanical energies may be treated with in this microscopic energies. To
make the case simpler, thermodynamics treat all kind of microscopic energies as the
“Internal Energy” of the system.

Some prominent kinds of energies are listed, as follows:

Thermal Energy:
Heat energy entering in to a system while making it hot, while it is cold or energy
leaving the system while making it cold, if it is hot is the thermal energy.
Mechanical Energy:
Energy produced while making some mechanical action like pressing a spring.
Kinetic Energy:
Energy produced due to molecular motion.
Potential Energy:
Energy produced or released due to the influence of some reference source like raising a
stone against gravitational attraction, stores a potential energy in stone.
Electrical Energy:
Energy produced due to some electrical potential difference like working of domestic
electrical appliances.
Magnetic Energy:
Energy due to magnetic force like movement of iron pin over a magnet.
Chemical Energy:
Energy due to chemical reaction like dry battery cells is the chemical energy.
 Nuclear Energy:
Energy librated by the nucleus particles, like nuclear reactors etc

A system may have more than one above listed energies, simultaneously; however the
thermodynamics treats such energies collectively and title it as “Total Energy” of the
system.

In thermodynamics, usually the problem is not concerned with summing of the various
energies of a system, but it studies the change in energies, if any, due to surroundings
changes.

Thermodynamics mainly treat the “thermal energy” of systems, which is directly related
with “heat” and other close relation with “temperature”

Heat:
Heat is a form of energy.

Heat energy is transferred between two systems (or a system and its surroundings) by
virtue of a temperature difference.

Heat energy can not be transferred between two bodies, if both are at same temperature
(may be taken as the necessary existence of electrical potential difference which give rise
to electrical energy. If there is no potential difference across two ends, no current flow and
hence no electrical energy flow).

Internal energy and heat energy are two different energies.

A body may have the internal energy (due to potential energy etc) but not having the heat
energy also.

Internal energy is associated with a state, while heat energy is associated with process.

Heat Measurement:
Work measurable in “Joules” units, is energy so as the energies in thermodynamics like
heat energy is measured in joules or British thermal unit (Btu). Joule is the unit in MKS
(SI) system whereas BTU is Standard English system.

The SI unit of work or energy, defined as, the work done by a force of one Newton acting
to move an object through a distance of one meter in the direction in which the force is
applied.
Equivalently, since kinetic energy is one half the mass times the square of the velocity, one
joule is the kinetic energy of a mass of two kilograms moving at a velocity of 1 m/s. This
is the same as 107 ergs (equal to the work done by a force of one dyne acting through a
distance of one centimeter) in the CGS system, or approximately 0.737 562 foot-pound in
the traditional English system.

In other energy units, one joule equals about 9.478 170 x 10-4 Btu, 0.238 846 calories, or
2.777 778 x 10-4 watt hour (energy delivered at a rate of one watt for a period of one hour
where one watt is the power produced by a current of one ampere flowing through an
electric potential of one volt). The joule is named for the British physicist James Prescott
Joule (1818-1889), who demonstrated the equivalence of mechanical and thermal energy,
experimentally in 1843.

1 watt = 0.001 341 02 horsepower (hp)

= 0.737 562 foot-pound per second (lbf/s).
In view of above definition, 1 joule work is done, if a force of 1 Newton applied to unit
mass to carry it away to 1 meter i.e.,
1 Joule = 1 Nm
Joule is a smaller unit and usually we come across with Kilo Joule (KJ)
1 Kilo Joule = 103 Joule

The amount of heat energy involved to raise or drop the temperature of 1 pound (mass) of
water at 68oF by 1oF, is 1 Btu.
1 Btu = 1.055 KJ

The amount of heat energy involved to raise or drop the temperature of 1 gram (mass) of
water from 14.5oC to 15.5oC, is 1 calorie.
1 cal = 3.969 x 10-3 Btu = 4.186 J
Problem # 31

Flow of Heat:
The best way to quantify the definition of heat is to consider the relationship between the
amount of heat added to or removed from a system and the change in the temperature of
the system.

As with work, the amount of heat transferred depends upon the path and not simply on the
initial and final conditions of the system. Also, as with work, it is important to distinguish
between heat added to a system from its surroundings and heat removed from a system to
its surroundings. A positive value for heat indicates that heat is added to the system by its
surroundings. The symbol (Q) is used to indicate the heat added to or removed from a
system per unit mass. The surrounding of under observation system is called the
environment.
If TE is the temperature of environment, TS be the temperature of the system and Q is the
heat energy concerned to the system then we may deduce the following relationship;
 If TS > TE, heat energy will flow from the system to the environment and hence (heat
flow out of the system)
Q < 0 or Q is -ive
 If TS = TE, heat energy will neither flow from the system to the environment or from
the environment to the system and hence Q = 0 or system is in thermal equilibrium
w.r.t. environment.
 If TS < TE, heat energy will flow from the environment to the system (heat flow in to
the system) and hence
Q > 0 or Q is +ive

Heat of Transformation:
Everyone is familiar with the physical phenomena that when a substance is heated, its
temperature increases, and when it is cooled, its temperature decreases. The heat added to
or removed from a substance to produce a change in its temperature is called sensible heat.

Another type of heat is called latent heat. Latent heat is the amount of heat added to or
removed from a substance to produce a change in phase. When latent heat is added, no
temperature change occurs.

There are two types of latent heat. The first is the latent heat of fusion given by LF. This is
the amount of heat added or removed to a unit mass of a substance to change phase
between solid and liquid (like the phase change from ice to water or water to ice). For
water at its normal freezing or melting temperature:

LF = 79.5 cal/g = 6..1kJ/mol = 333 kJ/kg

23
Where 1 mol = 6.02 x 10 elementary particles i.e., atoms or molecules

The second type of latent heat is the latent heat of vaporization given by LV. This is the
amount of heat added or removed to a unit mass of a substance to change phase between
liquid and gas (like the phase change from water to steam or steam to water). The latent
heat of vaporization is sometimes called the latent heat of condensation. For water at its
normal boiling or condensation temperature:

LV = 539 cal/g = 40.7kJ/mol =2256 kJ/kg

Specific Heat:
It may be experimentally observed that two different substances absorb different amount
of heat energies to get equally warm or to attain same temperature. For example we need
about 4.5 kJ energy to raise the temperature of 1kg iron from 20 to 30oC, where it takes
about 9 times this energy (41.8 kJ to be exact) to raise the temperature of 1 kg (mass) of
water by the same amount of temperature difference. This shows that energy absorption
capabilities are different for different materials or substances. This heat energy capability
is called “specific heat”. The specific heat is defined, as the energy required raising the
temperature of a unit mass of a substance by one degree and so the energy required raising
the temperature of one mole of a substance by one degree is called the molar specific heat.

Specific Heat of water = C = 1 cal/g oC = 1 Btu/lb oF = 4190 J/kg oK

This specific heat measurement gives different values of heat energies of one particular
sample substance, due to variation in pressure and volume, specifically dealing with gases.

This requires a little more modification in specific heat definition i.e., the energy required
raising the temperature of a unit mass of a substance by one degree at constant volume is
called the specific heat at constant volume (Cv) and the energy required raising the
temperature of a unit mass of a substance by one degree at constant pressure is called the
specific heat at constant pressure (Cp).

This is obvious that specific heat at constant pressure (Cp) is greater than specific heat at
constant volume (Cv) because at constant pressure the volume is allowed to increase and
some heat energy is utilized for performing the work for increasing the volume, beside
raising the temperature by one degree. So we have the relation:
Cp > Cv

For having a general expression for specific heat, we use the above definition i.e.,
Heat energy required = Specific heat ----- for unit mass ----- for one degree (from initial
temperature Ti to final temperature Tf )
Q = C (Tf - Ti ) For any unit mass
Q = C m (Tf - Ti ) For any mass “m”
Problem # 32
Problem # 33

Temperature and 1st Law of Thermodynamics:

Temperature is the property of a body or region of space that determines whether or not
there will be a net flow of heat into it or out of it from a neighboring body or region and in
which direction (if any) the heat will flow (heat flows from hot regions to cold regions).

If there is no heat flow the bodies or regions are said to be in thermal equilibrium and at
the same temperature. If there is a flow of heat, the direction of the flow is from the body
or region of higher temperature.
In a qualitative manner, we can describe the temperature of an object as that which
determines the sensation of warmth or coldness felt from contact with it.
It is easy to demonstrate that when two objects of the same material are placed together
(put in thermal contact), the object with the higher temperature cools while the cooler
object becomes warmer until a point is reached after which no more change occurs, and to
our senses, they feel the same. When the thermal changes stops, we say that the two
objects (or the systems) are in thermal equilibrium. We can then define the temperature of
the system by saying that the temperature is that quantity which is the same for both
systems when they are in thermal equilibrium.

If we experiment further with more than two systems, we find that many systems can be
brought into thermal equilibrium with each other; thermal equilibrium does not depend on
the kind of object used.

If two systems are separately in thermal equilibrium with a third, then they must also be in
thermal equilibrium with each other, and they all have the same temperature regardless of
the kind of systems they are.

The zeroth law of thermodynamics states that if three or more systems are in thermal
contact with each other and all in equilibrium together, then any two taken separately are
in equilibrium with one another.

Now one of the three systems could be an instrument calibrated (pre-defined or marked) to
measure the temperature - i.e. a thermometer. When a calibrated thermometer is put in
thermal contact with a system and reaches thermal equilibrium, we then have a
quantitative measure of the temperature of the system.

For example, a mercury-in-glass clinical thermometer is put under the tongue of a patient
and allowed to reach thermal equilibrium in the patient's mouth - we then see by how
much the silvery mercury has expanded in the stem and read the scale of the thermometer
to find the patient's temperature.

Measurement of Temperature – Thermometer

A thermometer is an instrument that measures the temperature of a system in a quantitative
way.

The principle of thermometer is based on the property of a substance, which shows distinct
in its appearance in a regular way with corresponding to changes in its temperature.

For example, the element mercury is liquid in the temperature range of -38.9° C to 356.7°
C. As a liquid, mercury expands, as it gets warmer, its expansion rate is linear and can be
accurately calibrated.
The mercury-in-glass thermometer illustrated in the above figure contains a bulb filled
with mercury that is allowed to expand into a capillary. Its rate of expansion is calibrated
on the glass scale.

Solids, liquids and gases are used as the thermometric substance i.e., the matter used to
measure the temperature.

In 1826, T. J. Seebeck, discovered that when wires of different metals are fused at one end
and heated, a current flows from one to the other. The electromotive force generated can
be quantitatively related to the temperature and hence, the system can be used as a
thermometer - known as a thermocouple. The thermocouple is used in industry and many
different metals are used - platinum and platinum/rhodium, nickel-chromium and nickel-
aluminum, for example. The National Institute of Standards and Technology (NIST)
maintain databases for standardizing thermometers.

In 1724, Gabriel Fahrenheit, an instrument maker of Amsterdam, used mercury as the

thermometric liquid. Mercury's thermal expansion is large and fairly uniform, it does not
adhere to the glass, and it remains a liquid over a wide range of temperatures. Its silvery
appearance makes it easy to read.

Fahrenheit described how he calibrated the scale of his mercury thermometer:

"Placing the thermometer in a mixture of sea salt-ice a point on the scale will be found
which is denoted as zero. A second point is obtained if the same mixture is used without
salt at laboratory working environment (room temperature) . Denote this position as 30. A
third point, designated as 96, is obtained if the thermometer is placed in the mouth so as to
acquire the heat of a healthy man." On this scale, Fahrenheit measured the boiling point of
water to be 212. Later he adjusted the freezing point of water to 32 so that the interval
between the boiling and freezing points of water could be represented by the more rational
number 180. Temperatures measured on this scale are designated as degrees Fahrenheit
(°F).

In 1780, J. A. C. Charles, a French physician, showed that for the same increase in
temperature, all gases exhibited the same increase in volume. Because the expansion
coefficient of gases is nearly the same, it is possible to establish a temperature scale based
on a single fixed point rather than the two fixed- point scales, such as the Fahrenheit and
Celsius scales. This brings us back to a thermometer that uses a gas as the thermometric
medium.

In 1871, Sir William Siemens, proposed a thermometer whose thermometric medium is a

metallic conductor whose resistance changes with temperature. The element platinum does
not oxidize at high temperatures and has a relatively uniform change in resistance with
temperature over a large range. The Platinum Resistance Thermometer is now widely used
as a thermoelectric thermometer and covers the temperature range from about -260° C to
1235° C.

Conversion of temperature Scales:

Following is the conversion relation among standard temperature measuring scales i.e.,
Kelvin, Celsius and Fahrenheit (ignore Rankine scale which is no more in use in
technology). The standard equivalence among the scales is given so as to have a better idea
of scales divisions.

Problem # 34