ALL RIGTHS RESERVED

Avoid to be example

2016

PREPARED BY:

JUMA A. MKIWA

DR. DOPPLER

jumamkiwa@yahoo.com

+255756547078/+255658083918

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 UNIT 1 Basic concepts of thermodynamics

Thermodynamic State

It is the state in which a thermodynamic system exists. Thermodynamic states are characterized
by a set of macroscopic properties, which determine the internal properties of a system in that state
and the interaction of the system with external bodies. These properties include temperature,
pressure, volume, electric polarization, and magnetization.

Thermal Equilibrium: When the temperature throughout a system is uniform, the system is in
thermal equilibrium.

Zeroth law of thermodynamics: The zeroth law of thermodynamics states that if two
thermodynamic systems are each in thermal equilibrium with a third, then all three are in thermal
equilibrium with each other.

If two systems A and B are separately in thermal equilibrium with a third system C, then the three
systems are in thermal equilibrium with each other. Zeroth law of thermodynamics states that two
systems which are individually in thermal equilibrium with a third one, are also in thermal
equilibrium with each other. This Zeroth law was stated by Flower much later than both first and
second laws of thermodynamics. This law helps us to define temperature in a more rigorous
manner.

Internal Energy - U is the most common symbol used for internal energy.
Internal energy is defined as the energy associated with the random, disordered motion of
molecules. It is separated in scale from the macroscopic ordered energy associated with moving
objects; it refers to the invisible microscopic energy on the atomic and molecular scale. For
example, a room temperature glass of water sitting on a table has no apparent energy, either
potential or kinetic . But on the microscopic scale it is a seething mass of high speed molecules
traveling at hundreds of meters per second. If the water were tossed across the room, this
microscopic energy would not necessarily be changed when we superimpose an ordered large scale
motion on the water as a whole.

FIRST LAW OF THERMODYNAMICS

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Concept of Heat

Heat may be defined as energy in transit.

Word heat is used only if there is a transfer of energy from one thermodynamic system to
another.

When two systems at different temperatures are kept in contact with each other than after
some time temperatures of both the systems become equal and this phenomenon can be
described by saying that energy has flown from one system to another.

This flow of energy from one system to another on account of temperature difference is
called heat transfer.

Flow of heat is a non-mechanical mode of energy transfer.

Heat flow depends not only on initial and find states but also on path it's.

P-V Indicator Diagram

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 Only two thermodynamic variables are sufficient to describe a system because third
variables can be calculated from equation of state of the system.

P-V Indicator Diagram is just a graph between pressure and volume of a system
undergoing an operation.

When a system undergoes an expansion from state A (P1 V1) to a state B (P2V2) its
indicator diagram is shown as follows.

In case of compression system at state A (P1 V1) goes

to a state B (P2V2) its indicator diagram is as follows.
Intermediate states of system are represented by
points on the curve.

The pressure volume curve for a fixed temperature is

called isotherm.

(a)Isothermal Process

In isothermal process temperature of the system remains

constant throughout the process.

For an Iso-thermal process equation connecting P, V

and T gives.
PV = constant
i.e., pressure of given mass of gas varies inversely with
its volume this is nothing but the Boyle's law.

In Iso thermal process there is no change in temperature, since internal energy for an
ideal gas depends only on temperature hence in iso thermal process there is no change in
internal energy.
Thus,
U=0
therefore, Q =W

Thus during iso thermal process

Heat added (or subtracted) from the system =
work done by (or on) the system

During isothermal expansion, Work done W = P

dV = +ve

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 During isothermal compression, Work done W = P dV = -ve

(b) Adiabatic Process

Process in which no heat enters or leaves a system is

called an adiabatic process.

For every adiabatic process Q=0

Prevention of heat flow can be accomplished by

surrounding system with a thick layer of heat insulating material like cork, asbestos etc.

Flow of heat requires finite time so if a process is performed very quickly then process
will be practically adiabatic.

On applying first law to adiabatic process we get

U=U2 - U1 and work done
W = P dV = P (V2-V1) = +Ve (adiabatic expansion)

Here, internal energy of systems decreases resulting a drop

in temperature. But, the
work done is positive.

On applying first law to adiabatic compression we get

U=U2 - U1 and work done
W = P dV = P (V2-V1) = -Ve (adiabatic compression)

Here, internal energy of systems increases resulting an increase in temperature. Bur, the work
done is negative.

(c) Isobaric Process

A process taking place at constant pressure is called isobaric process.

From equation (3) we see that work done in isobaric process is

W = P(V2 - V1) = nR (T2-T1)
where pressure is kept constant.

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 Here in this process the amount of heat given to the system is partly used in increasing
temperature and partly used in doing work.

(d) Isochoric process v:

In an isochoric process volume of the system remain uncharged throughout i.e. V = O.

When volume does not change no work is done ; W = 0 and therefore from first law
U2 - U1 = U =Q

All the heat given to the system has been used to increase the internal energy of the
system.

Work done in an isothermal expansion

Consider one mole of an ideal gas enclosed in a cylinder

with perfectly conducting walls and fitted with a
perfectly frictionless and conducting piston. Let P1, V1
and T be the initial pressure, volume and temperature of
the gas. Let the gas expand to a volume V2 when
pressure reduces to P2, at constant temperature T. At
any instant during expansion let the pressure of the gas
be P. If A is the area of cross section of the piston, then
force F = P A.

Let us assume that the pressure of the gas remains constant during an infinitesimally small outward
displacement dx of the piston.

Work done

dW = Fdx = PAdx = PdV

Total work done by the gas in expansion from initial volume V1 to final volume V2 is

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Work done in an adiabatic expansion

Consider one mole of an ideal gas enclosed in a cylinder with perfectly non conducting walls and
fitted with a perfectly frictionless, non-conducting piston. Let P1, V1 and T1 be the initial pressure,
volume and temperature of the gas. If A is the area of cross section of the piston, then force exerted
by the gas on the piston is F = P A, where P is pressure of the gas at any instant during expansion.
If we assume that pressure of the gas remains constant during an infinitesimally small outward
displacement dx of the piston, then work done

dW = F dx = P A dx

dW = P dV

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Adiabatic relations of system for perfect gas

Consider 1 gram of the working substance (ideal gas) perfectly insulated from the
surroundings. Let the external work done by the gas be W.
Applying the first law of thermodynamics

H = dU + W
But H = 0
and W = P.dV

Where P is the pressure of the gas and dV is the change in Volume.

0= dU + P dV .(1)

As the external work is done by the gas at the cost of its internal energy, there is fall in
temperature by dT.

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 dU = Cv dT

Therefore, Cv dT + P dV = 0 (2)

For an ideal gas, PV = rT

Differentiating, P dV + V dP = r dT
P dV + V dP
Therefore, dT =

Substituting the value of dT in equation (2)

Cv (P dV + V dP )
+ PdV = 0

Taking L.C.M.,
Cv (P dV + V dP )+ r P dV
=0

Therefore, Cv (P dV + V dP ) + r P dV = 0 ..(3)

Let r = Cp - Cv

Cv P dV + Cv V dP + Cp P dV Cv P dV = 0

Cv V dP + Cp P dV = 0

Dividing by Cv PV,

+ =0

Substitute
=

+ =0

Integrating,

log P + log V = Constant

log P + log = Constant

log P = Constant

or

P = Constant ..(4)

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This is the equation connecting pressure and volume during an adiabatic process.

Taking PV = r T

Or P =

Substitute in eqn (4)

= Constant

rT -1 = Constant

or

T -1 = Constant ..(5)

Taking PV = r T

Or V =

Substitute in eqn (4)

P( ) = Constant

= Constant
1

Or
1
= Constant (6)

Thus during adiabatic process,

(i) P = Constant
(ii) T -1 = Constant
1
(iii) = Constant

Reversible and irreversible processes

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8.9.1 Reversible process

A thermodynamic process is said to be reversible when (i) the various stages of an operation to
which it is subjected can be reversed in the opposite direction and in the reverse order and (ii) in
every part of the process, the amount of energy transferred in the form of heat or work is the
same in magnitude in either direction. At every stage of the process there is no loss of energy due
to friction, inelasticity, resistance, viscosity etc. The heat losses to the surroundings by
conduction, convection or radiation are also zero.

Condition for reversible process

(i) The process must be infinitely slow.

(ii) The system should remain in thermal equilibrium (i.e) system and surrounding should remain
at the same temperature.

Examples

(a) Let a gas be compressed isothermally so that heat generated is conducted away to the
surrounding. When it is allowed to expand in the same small equal steps, the temperature falls
but the system takes up the heat from the surrounding and maintains its temperature.

(b) Electrolysis can be regarded as reversible process, provided there is no internal resistance.

Irreversible process

An irreversible process is one which cannot be reversed back. Examples : diffusion of gases and
liquids, passage of electric current through a wire, and heat energy lost due to friction. As an
irreversible process is generally a very rapid one, temperature adjustments are not possible. Most
of the chemical reactions are irreversible.

Efficiency of Carnots cycle is independent of the working substance, but depends upon the
temperatures of heat source and sink.

Efficiency of Carnots cycle will be 100% if T1 = or T2 = 0 K. As neither the temperature of

heat source can be made infinite, nor the temperature of the sink can be made 0 K, the inference
is that the Carnot heat engine working on the reversible cycle cannot have 100% efficiency.

Relation between Cp and Cv (Meyers relation)

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Let us consider one mole of an ideal gas enclosed in a cylinder provided with a frictionless piston
of area A. Let P, V and T be the pressure, volume and absolute temperature of gas respectively
(Fig. 8.8). A quantity of heat dQ is supplied to the gas. To keep the volume of the gas constant, a
small weight is placed over the piston. The pressure and the temperature of the gas increase to P
+ dP and T + dT respectively. This heat energy dQ is used to increase the internal energy dU of
the gas. But the gas does not do any work (dW = 0).

dQ = dU = 1 Cv dT ... (1)

The additional weight is now removed from the piston. The piston now moves upwards through a
distance dx, such that the pressure of the enclosed gas is equal to the atmospheric pressure P. The
temperature of the gas decreases due to the expansion of the gas. Now a quantity of heat dQ is
supplied to the gas till its temperature becomes T + dT. This heat energy is not only used to increase
the internal energy dU of the gas but also to do external work dW in moving the piston upwards.

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13
 Unit 2

Second law of thermodynamics:

Statements -

Different scientists have stated this law in different ways to bring out its salient features.

(i) Kelvins statement

Kelvins statement of second law is based on his experience about the performance of heat
engine.

It is impossible to obtain a continuous supply of work from a body by cooling it to a temperature

below the coldest of its surroundings.

(ii) Clausius statement

It is impossible for a self acting machine unaided by any external agency to transfer heat
from a body at a lower temperature to another body at a higher temperature.

(iii) Kelvin - Plancks statement

It is impossible to construct a heat engine operating in a cycle, that will extract heat from a
reservoir and perform an equivalent amount of work.

Carnot theorem:

The efficiency of a reversible engine does not depend on the nature of the working substance. It
merely depends upon the temperature limits between which the engine works. "All the reversible
engines working between the same temperature limits have the same efficiency. No engine can be
more efficient than a carnot's reversible engine working between the same two temperatures."
Consider two reversible engines A and B, working between the temperature limits T1 and
T2 (Fig 1). A and B are coupled. Suppose A is more efficient than B. The engine A works as a heat
engine and B as a refrigerator. The engine A absorbs an amount of heat H1 from the source at a
temperature T1. It does external work W and transfers it to B. The more efficient engine (A) drive
the less efficient engine (B) as a heat pump. As the figure shows, this will cause heat to flow from
the cold to the hot reservoir without any external work or energy, which violates the second law
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of thermodynamics. The heat rejected to the sink is H2 at a temperature T2. The engine B absorbs
heat H2 from the sink at temperature T2 and W is the amount of work done on the working
substance. The heat given to the source at temperature T1 is H1.

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 Thus, for the two engines, A and B working as a coupled system, (H2 ' H2) is the quantity
of heat taken from the sink at a temperature T2 and (H1' H1) is the quantity of heat given to the
source at a temperature T1. Both (H2' H2) and (H1' H1) are positive quantities. It means heat
flows from the sink at a temperature T2 (lower temperature) to the source at a temperature T1
(higher temperature)i.e., heat flows from a body at a lower temperature to a body at a higher
temperature. But, no external work has been done on the system. This is contrary to the second
law of thermodynamics. Thus cannot be greater than . The two engines (reversible) working
between the same two temperature limits has the same efficiency. Moreover, in the case of a
Carnot's engine, there is no loss of heat due to friction, conduction or radiation (irreversible
possesses). Thus, the Carnot's engine has the maximum efficiency. Whatever may be the nature of
the working substance, the efficiency depends only upon the two temperature limits.

In a practical engine there is always loss of energy due to friction, conduction, radiation
etc., and hence its efficiency is always lower than that of a Carnot's engine.

Entropy:

(on a macroscopic scale) a function of thermodynamic variables, as temperature, pressure,

or composition, that is a measure of the energy that is not available for work during a
thermodynamic process. A closed system evolves toward a state of maximum entropy.

(in statistical mechanics) a measure of the randomness or measure of disorder of the system
of the microscopic constituents of a thermodynamic system. Symbol: S.

Principle of increase in entropy:

The entropy of the system never reduces. In the ideal process it can remain constant, but in
actual process the entropy of system and universe always increases.In actual practice the reversible
isentropic process never really occurs, it is only an ideal process. In actual practice whenever there

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is change in the state of the system the entropy of the system increases. Here are the various causes
of the increase in entropy of the closed system are:

1) Due to external interaction: In closed system the mass of the system remains constant but it
can exchange the heat with surroundings. Any change in the heat content of the system leads to
disturbance in the system, which tends to increase the entropy of the system.
2) Internal changes in the system: Due to internal changes in the movements of the molecules of
the system there is further disturbance inside the system. This causes irreversiblities inside the
system and an increase in its entropy.

The entropy of the isolated system is the measure of the irreversibility undergone by the system.
More is the irreversibility more increase is the entropy of the system. As such the reversible process
is an ideal process and it never really occurs. This means the certain amount of the irreversibility
is always there in the system, this also means that the entropy of the isolated system always goes
on increasing, it never reduces. Here let us keep in mind that isolated system can always be formed
by including any system and surroundings within a single boundary.

Entropy changes for an ideal gas:

Working : The Carnot engine has the following four stages of

operations. It is a reversible engine which converts heat energy into mechanical work.

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1. Isothermal expansion 2. Adiabatic expansion
3. Isothermal compression 4. Adiabatic compression

From A to B -

The cylinder is placed over the source which is at the temperature T1.
The piston is moved upward Pressure decreases and volume increases at constant
temperature T1.
The heat energy absorbed by the system is H1.
Gain in entropy of the working substance =

From B to C -

The cylinder is placed over the insulated stand

The piston is moved little upward Pressure decreases and volume increases at a decreased
temperature T2.
There is no heat energy absorbed by the system.
There is no change in entropy

From C to D -

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 The cylinder is placed over the sink which is at the temperature T2.

The piston is moved downward Pressure increases and volume decreases at constant

temperature T2.

The heat energy rejected by the system is H2.

Loss in entropy of the working substance =

From D to A -

The cylinder is placed over the insulated stand

The piston is moved little downward Pressure increases and volume decreases at an
increased temperature T1.
There is no heat energy absorbed by the system.

There is no change in entropy

1
Gain in entropy of the working substance =
1

2
Loss in entropy of the working substance = 2

Hence total change in entropy of the working substance in a complete reversible process
1 2
= 1
2
= 0

Increase in entropy in an irreversible process:

In an irreversible process like conduction or radiation, heat is lost by a body at a higher

temperature T1 and is gained by the body at a lower temperature T2. Here T1 is greater than T2. Let
the quantity of heat given out by a body at a temperature T1 be H. Consider the hot and cold bodies
as one system.

Loss in entropy of the hot body =
1

Gain in entropy of the cold body =
2

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Hence total increase in entropy of the working substance in a complete irreversible process

= 2
1

It is a positive quantity because T2 is less than T1. Thus the entropy of the system increases in all
irreversible processes.

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Entropy changes of Vander-waals gas:

A modification of the ideal gas law (PV = RT) was proposed by Johannes D. van der Waals in
1873 to take into account molecular size and inter molecular forces. It is usually referred to as the
van der Waals equation of state. Here, P Pressure, V- Volume, a - correction for
intermolecular force of attraction, b correction for molecular size and gas constant R
= 8.3145 J/mol K.

Two most important corrections neglected in the ideal gas are included.

We can calculate the total entropy change by integrating, first at constant and then at constant
:

The entropy at constant temperature and varying volume is given as follows:

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 Final entropy = Initial entropy + change in entropy

The entropy at varying temperature and constant volume is given as follows:

Final entropy = Initial entropy + Change in entropy

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Case 1 : For isothermal expansion b = 0 and T1 = T2

Therefore, the change in entropy becomes

Case 2 : For adiabatic process, let b =0 and

Therefore,

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 Therefore, = 0

Numerical Problems: Problem 1

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Problem 2:

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Problem 3

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Problem 4

UNIT -3

Schematic of a four stroke Otto engine

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 Suction (charge exchange stroke)
When the piston moves down, fuel/air mixture is drawn through the intake valve.
Compression (power stroke)
The cylinder volume is compressed.
Expansion (power stroke)
In the petrol engine, the fuel/air mixture is ignited by a spark plug.
Exhaust (charge exchange stroke)
The exhaust gas is expelled when the piston moves up.

Schematic of a four stroke diesel engine

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 Suction (charge exchange stroke)
When the piston moves down, air is drawn through the intake valve.
Compression (power stroke)
The cylinder volume is compressed.
Expansion (power stroke)
In the diesel engine fuel is injected under high pressure and the mixture ignites
spontaneously.
Exhaust (charge exchange stroke)
The exhaust gas is expelled when the piston moves up.

Differences between spark ignition engines (otto) and compression ignition (diesel)

Mechanically, there are no major differences between spark ignition engine and compression
ignition engines.

Basically are distinguished by their theoretical cycle. The spark ignition engine operates on the
Otto cycle and compression ignition as the diesel cycle.

The fundamental differences between the two types of engines are derived from the differences
in their cycles:

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introducing fuel into the engine

In most engines spark ignition (Otto cycle), air and fuel are introduced into the combustion
chamber in the form of gaseous mixture. The mixture is carried into the carburetor, and the
regulation of the quantity of mixture introduced is obtained by means of a butterfly valve.

In compression ignition engines (diesel cycle), air is introduced into the chamber through ducts
combusted will suction valve while the fuel is introduced directly by means of an injector. The air-
fuel mixture takes place in the combustion chamber, there is regulation of the amount of air, but
only a regulation of the amount of fuel added.

On the fuel

The spark ignition engine (Otto cycle) requires an ignition system to generate in the combustion
chamber a spark between the electrodes of a spark plug, in order that the combustion can be
initiated.

The compression ignition engine (diesel cycle) uses high temperature and pressure obtained by
compressing the air in the cylinder to begin combustion when the fuel is injected.

Compression ratio

The value of the compression ratio in spark ignition engines (Otto cycle) varies from 6-10, except
in exceptional cases, while in compression ignition engines (cycle diesel) ranges between 14 and
22.

In the spark ignition engine (Otto cycle), the upper limit of the compression ratio is essentially
determined by the fuel antiknock quality in the market for compression-ignition engines n (diesel
cycle) is determined mainly by the weight of the engine structure, which increases with increasing
compression ratio, of a special mode with large displacements.

Motor Weight

The compression ignition engine (diesel cycle) is usually heavier than a spark ignition engine (Otto
cycle) of the same capacity, because it works considerably higher pressure.

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Efficiency of Otto and diesel engines:

Diesel engines have never really caught on in passenger cars. During the late 1970's, diesel
engines in passenger cars did see a surge in sales because of the OPEC oil embargo (over half a
million were sold in the U.S.), but that is the only significant penetration that diesel engines have
made in the marketplace. Even though they are more efficient, there are eight historical problems
that have held diesel engines back:

1. Diesel engines, because they have much higher compression ratios (20:1 for a typical
diesel vs. 8:1 for a typical gasoline engine), tend to be heavier than an equivalent gasoline
engine.
2. Diesel engines also tend to be more expensive.
3. Diesel engines, because of the weight and compression ratio, tend to have lower
maximum RPM ranges than gasoline engines (see Question 381 for details). This makes
diesel engines high torque rather than high horsepower, and that tends to make diesel cars
slow in terms of acceleration.
4. Diesel engines must be fuel injected, and in the past fuel injection was expensive and less
reliable.
5. Diesel engines tend to produce more smoke and "smell funny."
6. Diesel engines are harder to start in cold weather, and if they contain glow plugs, diesel
engines can require you to wait before starting the engine so the glow plugs can heat up.

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 7. Diesel engines are much noisier and tend to vibrate.
8. Diesel fuel is less readily available than gasoline.

One or two of these disadvantages would be OK, but a group of disadvantages this large is a big
deterrent for lots of people.The two things working in favor of diesel engines are better fuel
economy and longer engine life.

Refregirator

A refrigerator is a cooling device. An ideal refrigerator can be regarded as Carnots heat

engine working in the reverse direction. Therefore, it is also called a heat pump. In a refrigerator
the working substance would absorb certain quantity of heat from the sink at
lower temperature and reject a large amount of heat to the source at a higher temperature
with the help of an external agency like an electric motor.

In an actual refrigerator vapours of freon (dichloro difluoro methane CCl2F2) act as the
working substance. Things kept inside the refrigerator act as a sink at a lower temperature T2. A
certain amount of work W is performed by the compressor (operated by an electric motor) on the
working substance. Therefore, it absorbs heat energy Q2 from the sink and rejects Q1 amount of
heat energy to the source (atmosphere) at a temperature T1.

Since this is a reversible cyclic process, the change in the internal

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energy of the working substance is zero (i.e) dU = 0

According to the first law of thermodynamics,

dQ = dU + dW

But dQ = Q2 - Q1

dW = -W and dU = 0

dQ = Q2 - Q1 = - W

Negative sign with W represents work is done on the system

(i.e) W = Q1 - Q2

Coefficient of performance

Coefficient of performance (COP) is defined as the ratio of quantity of heat Q2 removed per
cycle from the contents of the refrigerator to the energy spent per cycle W to remove this heat.

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Inferences

(i) Equation (1) shows that smaller the value of (T1 - T2) greater is the value of COP. (i.e.)
smaller is the difference in temperature between atmosphere and the things to be cooled, higher
is the COP.

(ii) As the refrigerator works, T2 goes on decreasing due to the formation of ice. T1 is almost
steady. Hence COP decreases. When the refrigerator is defrosted, T2 increases. Therefore
defrosting is essential for better working of the refrigerator.

Vapor compression regregirator:

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 A refrigerator has nine parts: a compressor, heat exchanging pipes both
inside and outside it, an expansion valve, a refrigerant, condenser coils, evaporator coils, a
condenser fan, and an evaporator fan. A compressor powers the whole process and an expansion
valve is a small length of pipe attached to the outside of the plastic food compartment. A
refrigerator transfer heat from the food compartment inside the refrigerator to the room outside
using a chemical called a Freon. Freon, the chemical that circulates around the refrigerator coils,
enters the narrow opening at one end of the expansion valve as a high-pressure liquid. The
expansion valve becomes wider along its length, so the pressure of the coolant falls as it travels
through the pipes. The drop in pressure causes the coolant to evaporate and become a cold low-
pressure gas, which is pumped into the evaporator coils inside the refrigerator. The cold gas in the
coils now absorbs heat from inside the refrigerator, causing the gas to warm up and the inside of
the refrigerator cool down. The warmed-up gas then flow to the condenser coils outside the
refrigerator, where the heat is combined into the air of the room.

Importance of Refrigerators in Our Everyday Lives

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 Refrigerators are one of the most valuable equipments found in our home today.
Almost every household in the world needs something to store their food to prevent them from
spoiling. This magical equipment which is craftily made turns on every five minutes and keeps
everything cold. Without it, there will be enormous amount of food that will go to be on the garbage
every day. Surely, such invention is great that it affects almost every people on earth regarding
whatever their walks of life are.

Natural preservatives used in the past are through salt and ice. This will relatively
lengthen and preserve the foods but they are not that easy to do and the preparations are delicate.
Today, refrigerators not only help us on preserving foods but also provide us a luxurious kind of
life. It keeps our beverage cool whenever we wanted them to, and it has freezer which relatively
make a fine desert that all of us are enjoying today.
How an air conditioner works

1. Warm air from

the room is sucked in
through a grille at the
base of the machine
2. The air flows over some chiller pipes through which a coolant fluid is circulating. This part
of the machine works just like the chiller cabinet in a refrigerator. It cools down the
incoming air and a dehumidifier removes any excess moisture.

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3. The air then flows over a heating element (similar to the one in a fan heater). On a hot day,
this part of the unit may be turned right up so the HVAC works as a heater.
4. A fan at the top blasts the air back through another grille into the room. If the heating
element is turned down, the air re-entering the room is much cooler, so the room gradually
cools down.
5. Meanwhile, coolant (a volatile liquid that evaporates easily) flows through the chiller pipes.
As it does so, it picks up heat from the air blowing past the pipes and evaporates, turning
from a cool liquid into a hotter gas. It carries this heat from inside the room to the outside
of the building, where it gives up its heat to the outside air. How? Just like in a refrigerator,
the coolant flows through a compressor unit and some condensing pipes, which turn it back
into a cool liquid ready to cycle round the loop again.
6. What happens to the heat? In the unit outside the building, there are lots of metal plates
that dissipate the heat to the atmosphere. An electric fan blows air past them to accelerate
the process.
7. Over time, the heat inside the building gradually pumps away into the outside air.

Uses of air conditioners:

Air Conditioning of Residential and Official Buildings

1. Most of the air conditioning units are devoted for comfort air conditioning that is meant to
provide comfortable conditions for people. Air conditioning of building is required in all
climates. In the summer, living/working spaces have to be cooled and in the winter the
same have to be heated. Even in places where temperature remains normal, cooling of the
building is required to remove the heat generated internally by people, lights, mechanical
and electrical equipment. Further in these buildings, for the comfort, humidity and
cleanliness of air has to be maintained. In hospitals and other medical buildings, conditions
on cleanliness and humidity are more stringent. There ventilation requirements often
specify the use of 100 percent outdoor air, and humidity limits.

Industrial Air Conditioning

2. The term industrial air conditioning refers to providing at least a partial measure of comfort
for workers in hostile environments and controlling air conditions so that they are favorable
to processing some objects or materials. Some examples of industrial air conditioning are
the following:

3. Spot Heating
In a cold weather it may be more practical to warm a confined zone where a worker is
located. One such approach is through the use of an infrared heater. When its surfaces are

37
 heated to a high temperature by means of a burner or by electricity, they radiate heat to the
affected area.

4. Spot Cooling
If a specific area has to be cooled, it will be unwise to cool entire room or factory. In this
case, conditions may be kept tolerable for workers by directing a stream of cool air onto
occupied areas.

Environmental Laboratories

The role of air conditioning may vary from one laboratory to the other. In one laboratory,
a very low temperature, say 40oC must be maintained to test certain equipment at low
temperatures, and in another, a high temperature and humidity may be required to study
behavior of animals in tropical climates.
5. Printing
In printing industries, control of humidity is a must. In some printing processes the paper
is run through several different passes, and air conditioning must be maintained to provide
proper registration. If the humidity is not properly maintained the problems of static
electricity, curling or buckling of paper or the failure of the ink to dry arise.

6. Textiles
Like paper, textiles are sensitive to changes in humidity and to a lesser extent changes in
temperature. In modern textile plants, yarn moves at very high speeds and any changes in
flexibility and strength of the yarn because of the change in humidity and temperature will
thus affect the production.

7. Precision Parts and Clean Rooms

In manufacturing of precision metal parts air conditioning helps to (a) keep the temperature
uniform so that the metal will not expand and contract, (b) maintain a humidity so that rust
is prevented and (c) filter the air to minimize dust.

8. Photographic Products
Raw photographic materials deteriorate fast in high humidity and temperatures. Other
materials used in coating film also require a careful control of temperature. Therefore,
photographic-products industry is a large user of refrigeration and air conditioning.

9. Computer Rooms
In computer rooms, air conditioning controls temperature, humidity and cleanliness of the
air. Some electronic components operate in a faulty manner if they become too hot. One
means of preventing such localized high temperature is to maintain the air temperature in
the computer room in the range of 20 to 23 0C. The electronic components in the computer
functions favorably at even lower temperatures, but this temperature is a compromise with
the lowest comfortable temperature for occupants. A relative humidity of about 65% is
maintained for comfort condition.

38
 10. Air Conditioning of Vehicles
For comfortable journey, planes, trains, ships, buses are air conditioned. In many of these
vehicles the major contributor to the cooling load is the heat from solar radiation and in
case of public transportation, heat from people.

11. Food Storage and Distribution

Many meats, fish, fruits and vegetables are perishable and their storage life can be extended
by refrigeration. Fruits, many vegetables and processed meat, such as sausages, are stored
at temperatures just slightly above freezing to prolong their life. Other meats, fish,
vegetables and fruits are frozen for many months at low temperatures until they are
defrosted and cooked by consumer.

Numerical Problems:

1)

39
2)

40
41
 Unit 4

Andrews' experiments with carbon dioxide

In our consideration of ideal gases in previous modules we have assumed that forces between
molecules forces are zero and therefore that they follow the kinetic theory of gases exactly. This
is not the case with actual gases, however.

A gas which follows the gas laws precisely is known as an ideal gas and one which does not is
called a real gas.

In 1847 Regnault constructed PV curves up to 400 (4x 107 Pa) atmospheres and found that Boyle's
law was not obeyed at these high pressures. Amagat went a stage further in 1892, working with
nitrogen to pressures of some 3000 atmospheres (3 x 108 Pa) down a coal mine.

The idea that actual gases did not always obey the ideal gas equation was first tested by Cagniard
de la Tour in 1822, using the apparatus shown in Figure.

A liquid such as water or ether was trapped in a tube and the end of the tube placed in a bath
whose temperature could be controlled. The temperature was then varied and the behaviour of the
liquid observed. The space above the liquid is obviously filled with vapour and it was noticed that
at a particular temperature no difference could be seen between the liquid and vapour states this

42
was called the critical temperature. This phenomenon was not predicted by Boyle's law, which
says nothing about the liquefaction of gases.

Thomas Andrews, in 1869, experimented with carbon dioxide gas to try to turn it into liquid carbon
dioxide by applying high pressures. He enclosed two gas volumes, one of Nitrogen and one of
carbon dioxide, in two identical tubes. Each volume was enclosed by a short thread of mercury
and the tubes were sealed into a metal compression chamber. In the chamber, pressure was applied
to a volume of water by screwing in pressure plungers. The high pressures developed in the water
volume were transmitted to the two gas volumes. The pressures developed in the water and in the
gas volumes were identical. By studying the movement of mercury threads in the Nitrogen and the
carbon dioxide tubes as pressure was increased the changes in gas volume were found. By
measuring the change in length of the Nitrogen column, the Nitrogen pressure (which was the
same as the carbon dioxide pressure) was found. The capillary tubes were very strong and Andrews
obtained results up to pressures of 107 Pa. The results are shown in the two graphs in Figure 2.
Above about 50 oC Boyle's law was fairly closely obeyed. But as you can see the behavior of the
'gas' is different above and below about 30 oC - in fact Andrews found that the critical temperature
for carbon dioxide was 30.9 oC.By squeezing the water volume, and watching the positions of the
two mercury threads, both the volume and the pressure of carbon dioxide could be found.

Andrews conducted a number of experimental 'runs' and plotted values of volume for different
values of pressure, each 'run' being at a definite fixed temperature. So for each temperature he
obtained a curve of volume, V, against pressure, P. Such curves, found for definite temperatures,
are known as isothermals (same temperature).

Andrews found that he was able to liquefy carbon dioxide as he expected but only if the gas
temperature was below a definite value. Liquid carbon dioxide was obtained only if the gas was
first cooled below a temperature of 31.1C, no matter how high the pressure applied. This
temperature is called the critical temperature of carbon dioxide. It was later found that each gas
has its own critical temperature and it was impossible to turn it into a liquid by compression unless
it was first cooled below this temperature.

43
Above this temperature carbon dioxide could not be liquefied by pressure alone, while below this
temperature an increase in pressure would finally result in liquid carbon dioxide. At the critical
point the gas and liquid are in equilibrium.

Liquefaction of gases

Vapor, liquid, solid these are the three phases that a gas passes through as it is cooled. The
molecules in a gas are in constant motion, and the higher the temperature, the greater the speeds
of the molecules in the gas. As the gas is cooled at a constant pressure the molecules slow down,
and the gas occupies a smaller volume. As the average distance between molecules becomes
smaller, the forces of attraction between molecules become great enough for them to be bound
together in a loose sort of way. The gas has become a liquid.

Another way of thinking of this liquefaction process is to remember that all molecules in a liquid
exert a force of attraction to each other. At high temperatures the kinetic energies (the energies of
movement) of the molecules are big enough for the forces of attraction to be overcome. When
the kinetic energies of the molecules are reduced with the drop in temperature, the molecules can
hold together in the liquid. Apart from cooling a gas, another method of liquefying it is to apply a
high pressure.

What happens when a gas is compressed? When gas is cooled, it can change into a liquid
because the average distance of separation of molecules becomes small, and the molecular
energies are not big enough to enable the molecules to overcome the cohesive forces. Exactly the
same two things happen when the gas is compressed. The gas occupies a smaller volume so the
average distance between molecules must be smaller. In addition, the energies of the molecules
become smaller when the gas is compressed.

If the end of a bicycle pump is stopped and the plunger pressed, the gas inside the cylinder heats
up. If the plunger is then fixed, and the gas allowed to cool down to the temperature of its

44
surroundings, the gas has lost heat energy. But the temperature of the gas is the same as it was
before the gas was compressed. The energy has lost internal energy because the molecules have
been forced closer together as a result of the compression process. Gases can lose internal energy
by compression, so it is possible to liquefy the gas using this process.

These ideas form the basis for a useful definition of a vapour:

A vapour is a gas below its critical temperature

Some critical temperatures are shown in the following table.

Substance Critical temperature (oC) Boiling point (oC)

Helium -268 -269
Hydrogen -240 -253
Nitrogen -147 -196
Air -140 -190
Oxygen -118 -183
Carbon dioxide 30.9 -78.2
Chlorine 146 -34
Water 374 100

To liquefy a gas by pressure alone it must first be cooled below its critical temperature.

Amagat's law or the Law of Partial Volumes of 1880 describes the behaviour and properties of
mixtures of ideal (as well as some cases of non-ideal) gases. Of use in chemistry and
thermodynamics, Amagat's law states that the extensive volume V = Nv of a gas mixture is equal
to the sum of volumes Vi of the K component gases, if the temperature T and the pressure p remain
the same:[1][2]

This is the experimental expression of volume as an extensive quantity. It is named after Emile
Amagat.

According to Amagats law of partial volume, the total volume of a non-reacting mixture of gases
at constant temperature and pressure should be equal to the sum of the individual partial volumes

45
of the constituent gases. So if are considered to be the partial volumes of
components in the gaseous mixture, then the total volume would be represented as:

When two or more pure gases, held at a temperature T and a pressure p, are mixed to form a
homogeneous gas mixture at the same temperature and total pressure, the relationship between the
volume of the mixture and the volume of the pure components is, generally, complicated.
However, if the pure components and the mixture conform to the perfect gas equation of state then
the volume of the mixture is simply the sum of the volumes of the pure components [Bett et al.
(1975)] so that

This result is known as Amagat's Law of Additive Volumes. While it is strictly valid only for the
mixing of perfect gases, the law is often a useful approximation for real gases.

46
47
 Helmholtz Free Energy

Four quantities called "thermodynamic potentials" are useful in the chemical thermodynamics of
reactions and non-cyclic processes. They are internal energy, the enthalpy, the Helmholtz free
energy and the Gibbs free energy. The Helmholtz free energy F is defined by

48
The internal energy U might be thought of as the energy required to create a system in the absence
of changes in temperature or volume. But if the system is created in an environment of temperature
T, then some of the energy can be obtained by spontaneous heat transfer from the environment to
the system. The amount of this spontaneous energy transfer is TS where S is the final entropy of
the system. In that case, you don't have to put in as much energy. Note that if a more disordered
(higher entropy) final state is created, less work is required to create the system. The Helmholtz
free energy is then a measure of the amount of energy you have to put in to create a system once
the spontaneous energy transfer to the sytem from the environment is accounted for.

The four thermodynamic potentials are related by offsets of the "energy from the environment"
term TS and the "expansion work" term PV. A mnemonic diagram suggested by Schroeder can
help you keep track of the relationships between the four thermodynamic potentials.

Relating Helmholtz Energy to Gibbs Energy

The Helmholtz Energy is given by the equation:

A=UTS

It is comparable to Gibbs Energy in this way:

G=A+PV

The Helmholtz Energy is used when having a constant pressure is not feasible.

Along with internal energy and enthalpy, the Helmholtz Energy and Gibbs Energy make up the
quad group called the thermodynamic potentials; these potentials are useful for describing
various thermodynamic events. A mnemonic device has been created for your memorizing
pleasure:

49
TS represents energy from surroundings, and PV represents work in expansion. If needed, refer
to the links above to refresh your memory on enthalpy and internal energy.

Gibbs Free Energy

Four quantities called "thermodynamic potentials" are useful in the chemical thermodynamics of
reactions and non-cyclic processes. They are internal energy, the enthalpy, the Helmholtz free
energy and the Gibbs free energy. The Gibbs free energy G is defined by

The internal energy U might be thought of as the energy required to create a system in the absence
of changes in temperature or volume. But as discussed in defining enthalpy, an additional amount
of work PV must be done if the system is created from a very small volume in order to "create
room" for the system. As discussed in defining the Helmholtz free energy, an environment at
constant temperature T will contribute an amount TS to the system, reducing the overall investment
necessary for creating the system. This net energy contribution for a system created in environment
temperature T from a negligible initial volume is the Gibbs free energy.

The change in Gibbs free energy, G, in a reaction is a very useful parameter. It can be thought of
as the maximum amount of work obtainable from a reaction. For example, in the oxidation of
glucose, the change in Gibbs free energy is G = 686 kcal = 2870 kJ. This reaction is the main
energy reaction in living cells. Example: Electrolysis of water Hydrogen fuel cell G as indicator
of spontaneity of chemical reactions Relationship of G to standard electrode potentials

Gibbs free energy

The Gibbs Energy is named after a Josiah William Gibbs, an American physicist in the late 19th
century who greatly advanced thermodynamics; his work now serves as a foundation for this
branch of science. This energy can be said to be the greatest amount of work (other than expansion
work) a system can do on its surroundings, when it operates at a constant pressure and temperature.

First, a modeling of the Gibbs Energy by way of equation:

50
 G=U+PVTS

Where:

U= Internal Energy
TS = absolute temperature x final entropy
PV = pressure x volume

Of course, we know that U+PV can also be defined as:

U+PV=H

Where:

H is change in enthalpy

Which leads us to a form of how the Gibbs Energy is related to enthalpy:

G= HTS

All of the members on the right side of this equation are state functions, so G is a state function
as well. The change in G is simply:

G=HTS

- Gibbs free energy (available energy)

- Change in enthalpy (change in Potential energy enthalpy is the change in energy

possessed by the system)

T Temperature

S change in entropy

Case 1: Change in enthalpy for spontaneous process A boy sliding down in a slide Here
Potential energy decreases and hence the enthalpy decreases

H H

Case 2: Change in entropy for spontaneous process: Diffusion of gases when gases enter in to
another medium, the randomness increases and thereby the entropy increases
51
 s S

Case 3: Change in temperature for spontaneous process : Inflated balloon at room temperature
doesnt burst when it is heated, the temperature of the gas molecules get increased and due to
expansion of gases inside the balloon, it gets burst.

T T

Substituting the values of above three cases in the first eqn, the Gibbs energy will be negative

Ie, < 0

In the case of oxidation of glucose in our body, brings carbon dioxide and water.

Here, the Gibbs energy will be positive

Ie, > 0

Reasoning Behind the Equation

As a quick note, let it be said that the name "free energy", other than being confused with another
energy exactly termed, is also somewhat of a misnomer. The multiple meanings of the word "free"
can make it seem as if energy can be transferred at no cost; in fact, the word "free" was used to
refer to what cost the system was free to pay, in the form of turning energy into work.

is useful because it can tell us how a system, when we're given only information on it, will act.

G<0

indicates a spontaneous* change to occur.

G>0

indicates an absence of spontaneousness.

G=0

indicates a system at equilibrium.

It was briefly mentioned that G is the energy available to be converted to work. The definition
is self evident from the equation.

52
Look at

G=HTS. Recall that H is the total energy that can be made into heat.

TS

is the energy not available to be converted to work. By a reordering of the Gibbs Energy
equation:

H=GTS

Expressed in words:

the energy available to be turned into heat = G- the energy that is not free to do work. This lets
us see that G MUST be the energy free to do work.

Why constant temperature and pressure? It just so happens that these are regularly occurring
factors in the laboratory, making this equation practical to use, and useful as well, for chemists.
An example of Gibbs Energy in the real world is the oxidation of glucose; G in this case is equal
to 2870 kJ, or 686 Calories. For living cells, this is the primary energy reaction.

Reduced equation of state

Cubic equations of state are called such because they can be rewritten as a cubic function of Vm.

The Van der Waals equation of state may be written:

_________________(A)

where is molar volume. The substance-specific constants a and b can be calculated from
the critical properties and (noting that is the molar volume at the critical point) as:

__________________ (1)

___________________ (2)

RTc = 8Pcb _________________(3)

The van der Waals equation may be considered as the ideal gas law, "improved" due to two
independent reasons:

53
 1. Molecules are thought as particles with volume, not material points. Thus cannot be
too little, less than some constant. So we get ( ) instead of .
2. While ideal gas molecules do not interact, we consider molecules attracting others within
a distance of several molecules' radii. It makes no effect inside the material, but surface
molecules are attracted into the material from the surface. We see this as diminishing of
pressure on the outer shell (which is used in the ideal gas law), so we write ( something)
instead of . To evaluate this something, let's examine an additional force acting on an
element of gas surface. While the force acting on each surface molecule is ~ , the force

acting on the whole element is ~ ~ .

With the reduced state variables, i.e.

Vr=Vm/Vc ________________(4)

Pr = P/Pc ___________(5)

Tr=T/Tc ________________(6)

The reduced form of the Van der Waals equation can be formulated:

Substituting equations 1, 2,3,4,5 and 6 in 1,

3 2
(PcPr + 22 ) (VcVr- ) = RTrTc
3

3
(PcPr + 2 ) (VcVr - ) = Tr 8Pcb (using eqn 3)
3

3
(PcPr + 2 ) (VcVr - ) = Tr 8Pc (using eqn 2)
3 3

3 1
Pc (Pr+ 2 ) Vc ( Vr - 3 ) = 8Tr Pc
3

3 ( 3 1)
Pc (Pr+ 2 ) Vc = 8Tr Pc
3 3

3
(Pr+ 2 ) (3Vr-1) = 8Tr

The above equation is the reduced Vander waals equation of state

Vander waals equation of state

The ideal gas equation is PV = RT

54
Here, the size of the gas molecules were considered to be negligible and the inter-molecular
force of attraction are absent.

But, in practice, at high pressure, the size of gas molecules becomes significant when compared
to its volume.

Also, at high pressure, the molecules come closer to each other and inter-molecular force of
attraction becomes appreciable.

Hence Vander-waals made some correction for pressure and volume in the ideal gas equation.

Correction for Pressure:

The correction for pressure depends upon

(i) The number of molecules striking the walls of the container/sec.

(ii) The number molecules present/unit volume.

Both these factors depends on density

= m/v
1
Therefore, P 2

Or

P= _______________ (1)
2

Correction for volume

4
Volume of each molecule = 3 3 = x ___________ (2)

The sphere of influence of the molecule with respect to the nearest

molecules

4
S = 3 (2r)3

4
S=8( 3 )
3

using eqn 2,

S = 8x _____________ (3)

Let the volume available for the first molecule = V

55
The volume available for the second molecule = V- S

The volume available for the third molecule = V 2S

The volume available for the nth molecule = V- (n-1) S

Therefore, the average volume occupied by the molecules

= - {1 + 2 + + (n 1)}

(n1)
= V- { }
2

= V- -2
2

Let S/2 = 0

= V- 2

We know S = 8x from equation 3.

Substituting the value of S in the above equation,

8
= V- 2

= V- 4xn

= V-b __________________ (4)

Where b = 4xn

Therefore, equation 4 is the correction for volume.

Therefore, Vanderwaals gas equation becomes,

( P + 2 ) (V-b) = RT

56
Critical Constants

The critical temperature, Tc, is characteristic of every gas and may be defined as: The
temperature below which the continuous increase of pressure on a gas ultimately brings about
liquefaction and above which no liquefaction can take place no matter what so ever pressure be
applied.

The pressure required to liquefy the gas at critical temperature is called critical pressure and the
volume occupied by 1 mole of gas under these conditions is called the critical volume.

Condition to find critical constants

()T = 0 and

( )T = 0

If the solution of the above equations becomes zero or infinity then there exists a critical point.
Critical point is the point at which the gas changes its state with respect to change in pressure and
volume.

Critical Temperature Tc =

Critical pressure Pc =

Critical Volume Vc = 3b

Enthalpy: Enthalpy is the amount of heat content used or released in a system at constant
pressure (or) energy released or absorbed during a chemical reaction.

Enthalpy: is a defined thermodynamic potential, designated by the letter "H", that consists of
the internal energy of the system (U) plus the product of pressure (p) and volume (V)
of the system.

Entropy: Degree of disorderness of the system.

Internal energy E: which is the sum of the kinetic and potential energies of the particles that
form the system.

57
 UNIT 5

THERMOMETRY

Temperature
Temperature is a measure the sensation of warmth or coldness of an object, felt from contact
with it. This sensation of touch gives an approximate or relative measure of the temperature.
Temperature is measured in different scales, including Fahrenheit (F) and Celsius (or centigrade,
C). The units of the Fahrenheit and Celsius scales are called degrees and are denoted by .
Swedish astronomer Anders Celsius devised the Celsius scale in 1742. He fixed the 0 of the
scale at the freezing of water, and the 100 at the boiling of water.

Themometer
A thermometer is used to measure the temperature of an object it is used to find how cold or
hot the object is. Galileo invented a rudimentary water thermometer in 1593. He called this
device a "thermoscope". However, this form was ineffective as water freezes at low
temperatures.

In 1714, Gabriel Fahrenheit invented the mercury thermometer, the modern thermometer. The
long narrow uniform glass tube is called the stem of a thermometer. The small tube called the
bulb, which contains mercury. Mercury is toxic, and it is very difficult to dispose it when the
thermometer breaks. So, nowadays digital thermometers are used to measure the temperature, as
they do not contain mercury.

Types of Thermometers
There are different types of thermometers that measure the temperatures of different things like
air, our bodies, food and many other things. There are clinical thermometers, laboratory
thermometers, Galileo thermometers and digital remote thermometers. Among these, the
commonly used thermometers are clinical thermometers and laboratory thermometers.

Clinical Thermometer:
These thermometers are used to measure the temperature of the human body, at home, clinics
and hospitals. All clinical thermometers have a kink that prevents the mercury from falling down
rapidly so that the temperature can be noted conveniently. There are temperature scales on either
side of the mercury thread, one in Celsius scale and the other in Fahrenheit scale.

A clinical thermometer indicates temperatures from 35 C to 42 C or from 94 F to 108 F.

To note a reading, place the thermometer in the persons mouth. Since the Fahrenheit scale is
more sensitive than the Celsius scale, body temperature is measured in degrees Fahrenheit only.

58
A healthy persons average body temperature is between 98.6 F and 98.8 F .

Precautions:
Wash the thermometer before and after use with an antiseptic solution, and handle it with
care.
See that the mercury levels are below the kink and dont hold the thermometer near its bulb.
While noting down the reading in the thermometer, place the mercury level along the eye
sight.
Do not place the thermometer in a hot flame or in the hot sun.

Laboratory Thermometers
These thermometers are used to measure the temperature in school and other laboratories for
scientific research. They are also used in the industry as they can measure temperatures higher
than what clinical thermometers can record. The stem and the bulb are longer when compared to
that of a clinical thermometer. A laboratory thermometer has only the Celsius scale ranging from
-10o C to 110 o C.

Precautions:
A laboratory thermometer doesnt have a kink.
Do not tilt the thermometer. Place it upright.
Note the reading only when the bulb has been surrounded by the substance from all sides.

Conversion
The Celsius and Fahrenheit scales are related as C /5 = F - 32 /9 = K 32/ 5 .

Heat Temparature

1. Heat is a form of energy 1. Temperature is a quantity which

obtained due to random motion of determaines the direction of flow of heat on
molecules in a substance. keeping the two bodies at different
temperatures in contact.

2. The S.I. unit of heat is joule (J). 2. The S.I. unit of temperature is kelvin (K).

3. The amount of heat contained in 3. The temperature of a body depends on the

a body depends on average kinetic energy due to random motion
temperature, mass and material of of its molecules.
body.
4. Temperature is a measured by a
4. Heat is measured using the thermometer directly.

59
 principle of calorimetry.
5. Two bodies at same temperature may
5. Two bodies having same differ in the quantities of heat contained in
quantity of heat may deffer in thier them.
temperature.
6. When two bodies at different temperatures
6. When two bodies areplaced in are placed in contact, the resultant
contact, the total amount of heat is temperature is a temperature in between the
equal to the sum of heat of two temperatures.
individual body.

Properties of the Thermometric Liquid:

A Thermometric liquid must have the following properties:

Thermometric Liquid should be easily available in pure state.

Thermometric Liquid should exert low vapour pressure.

Thermometric Liquid should be a good conductor of heat.

Thermometric Liquid should have a uniform rate of expansion, such that a linear scale
can be easily marked.

Thermometric Liquid should have large expansion for a unit degree rise in temperature,
so that its expansion is visible to the naked eye.

Thermometric Liquid should be shiny and opaque so that it is clearly visible in glass.

Thermometric Liquid should have a high boiling point and low freezing point, so that a
wide range of temperature changes could be recorded by a single thermometer.

Thermometric Liquid should not stick to the sides of the glass tube.

Thermometric Liquid should have low specific heat capacity, so that it rapidly attains the
temperature of a given substances, without absorbing any appreciable amount of heat
energy from it.

Mercury as a Thermometric Liquid:

Mercury fulfils practically all the requisites of a thermometric liquid as the following:

60
 Mercury does not stick to the sides of the glass.

Mercury exerts very low vapour pressure.

Mercury is a good conductor of heat.

Mercury has low specific heat capacity.

Mercury expands uniformly.

Mercury is easily available in pure state..

Mercury is an opaque and shinning liquid metal.

IMercury has a high b.p. (357C) and low m.p (- 39C)

Disadvantages of mercury as Thermometric Liquid:

Mercury freezes below -39C and hence, it cannot be used in very cold regions like
Antarctic or Arctic.

Mercury's expansion is not very large for 1C rise in temperature and hence, very small
changes in temperature cannot be measured.

Alcohol as Thermometric Liquid:

Alcohol can be coloured brightly and hence, is easily visible.

Alcohol freezing point is below -100C and hence, can record very low temperatures.

Alcohol's expansion per degree centigrade rise in temperature is very large and hence,
very sensitive thermometers can be made with it.

Disadvantages of Alcohol as Thermometric Liquid:

Alcohol has a high vapour pressure.

Alcohol sticks to the sides of glass.

Alcohol has high specific heat capacity.

Alcohol can not be used for measuring high level temperatures as alcohol boils at 78C.

Alcohol is difficult to obtain pure alcohol.

61
 Alcohol is not good conductor of heat.

Disadvantages of Water as Thermometric Liquid:

Water sticks to the sides of glass.

Water is transperant.
Water evaporates under vaccum conditions.
Water does not expand uniformly.
Water has highest specific heat capacity (4.2 J/gK)
Expansion of water per degree rise in temperature is very small.
Water cannot be obtained in pure form easily.
Melting point of water is 0C and boiling point is 100C . Thus , the temperatures less
than 0C and more than 100C cannot be measured.
Water is a bad conductor of heat.

The Constant-Volume Gas Thermometer and the Absolute Temperature Scale

The temperature readings given by a gas thermometer are nearly independent of the substance used
in the thermometer. One version is the constant-volume gas thermometer shown in Figure . The
physical change exploited in this device is the variation of pressure of a fixed volume of gas with
temperature. When the constant-volume gas thermometer was developed, it was calibrated by
using the ice and steam points of water, as follows (a different calibration procedure, which we
shall discuss shortly, is now used): The flask was immersed in an ice bath, and mercury reservoir
B was raised or lowered until the top of the mercury in column A was at the zero point on the
scale. The height h, the difference between the mercury levels in reservoir B and column A,
indicated the pressure in the flask at 0C.

62
Figure. constant-volume gas thermometer measures the pressure of the gas contained in the flask
immersed in the bath. The volume of gas in the flask is kept constant by raising or lowering
reservoir B to keep the mercury level in column A constant.

The flask was then immersed in water at the steam point, and reservoir B was readjusted until the
top of the mercury in column A was again at zero on the scale; this ensured that the gass volume
was the same as it was when the flask was in the ice bath (hence, the designation constant
volume). This adjustment of reservoir B gave a value for the gas pressure at 100C. These two
pressure and temperature values were then plotted, as shown in Figure. The line connecting the
two points serves as a calibration curve for unknown temperatures. If we wanted to measure the
temperature of a substance, we would place the gas flask in thermal contact with the substance
and adjust the height of reservoir B until the top of the mercury column in A was at zero on the
scale. The height of the mercury column would indicate the pressure of the gas; knowing the
pressure, we could find the temperature of the substance using the graph in Figure.

63
Figure . A typical graph of pressure versus temperature taken with a constant-volume gas
thermometer. The two dots represent known reference temperatures (the ice and steam points of
water).

Now let us suppose that temperatures are measured with gas thermometers containing different
gases at different initial pressures. Experiments show that the thermometer readings are nearly
independent of the type of gas used, as long as the gas pressure is low and the temperature is well
above the point at which the gas liquefies. The agreement among thermometers using various
gases improves as the pressure is reduced.

If you extend the curves shown in Figure toward negative temperatures, you find, in every case,
that the pressure is zero when the temperature is -273.15C. This significant temperature is used
as the basis for the absolute temperature scale, which sets -273.15C as its zero point. This
temperature is often referred to as absolute zero. The size of a degree on the absolute temperature
scale is identical to the size of a degree on the Celsius scale. Thus, the conversion between these
temperatures is

where TC is the Celsius temperature and T is the absolute temperature. Because the ice and steam
points are experimentally difficult to duplicate, an absolute temperature scale based on a single
fixed point was adopted in 1954 by the International Committee on Weights and Measures. From
a list of fixed points associated with various substances (Table), the triple point of water was
chosen as the reference temperature for this new scale. The triple point of water is the single
combination of temperature and pressure at which liquid water, gaseous water, and ice (solid
water) coexist in equilibrium. This triple point occurs at a temperature of approximately 0.01C
and a pressure of 4.58 mm of mercury. On the new scale, which uses the unit kelvin, the
temperature of water at the triple point was set at 273.16 Kelvin, abbreviated 273.16 K. (Note: no
degree sign is used with the unit Kelvin.) This choice was made so that the old absolute
temperature scale based on the ice and steam points would agree closely with the new scale based
on the triple point. This new absolute temperature scale (also called the Kelvin scale) employs the

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SI unit of absolute temperature, the kelvin, which is defined to be 1/273.16 of the difference
between absolute zero and the temperature of the triple point of water.

The value of P is used to calculate the temperature. Temperature is calculated using the formula

T = aP + b

Where a is the constant of ice at 0oC and b is constant of steam at 100oC.

Figure shows the absolute temperature for various physical processes and structures. The
temperature of absolute zero (0 K) cannot be achieved, although laboratory experiments

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incorporating the laser cooling of atoms have come very close.

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What would happen to a gas if its temperature could reach 0 K? As Figure indicates, the pressure
it exerts on the walls of its container would be zero. Thus, according to classical physics, the kinetic
energy of the gas molecules would become zero at absolute zero, and molecular motion would
cease; hence, the molecules would settle out on the bottom of the container. Quantum theory
modifies this model and shows that some residual energy, called the zero-point energy, would
remain at this low temperature.

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1

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A thermometer is calibrated by using two objects of known temperatures. The typical process
involves using the freezing point and the boiling point of pure water. Water is known to freeze at
0C and to boil at 100C at an atmospheric pressure of 1 atm. By placing a thermometer in mixture
of ice water and allowing the thermometer liquid to reach a stable height, the 0-degree mark can
be placed upon the thermometer. Similarly, by placing the thermometer in boiling water (at 1 atm
of pressure) and allowing the liquid level to reach a stable height, the 100-degree mark can be
placed upon the thermometer. With these two markings placed upon the thermometer, 100 equally
spaced divisions can be placed between them to represent the 1-degree marks. Since there is a
linear relationship between the temperature and the height of the liquid, the divisions between 0
degree and 100 degree can be equally spaced. With a calibrated thermometer, accurate
measurements can be made of the temperature of any object within the temperature range for which
it has been calibrated.

What is the use of kink in the clinical thermometer?

In a thermometer, the mercury moves up and down the capillary tube as the temperature changes
and if it is removed then it form contact with the patient and the reading would steadily fall as it
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cooled. As a medical thermometer to get the reading of the patient's temperature even after it has
been removed from the patient, we need to stop the mercury shrinking back into the reservoir. The
kink in the clinical thermometer does this, it breaks the connection between the mercury in the
capillary and the reservoir. So the reading given is accurate. Before it can be used again the
mercury in the capillary has to be vigorously shaken back into the reservoir.

The glass around the bulb in a clinical thermometer (the conventional one) is thin because glass is
not a good conductor of heat. The clinician and the patient don't want to wait half an hour to get a
good temperature reading. By using the thinner glass, the transfer of heat into the thermometer's
fluid will be more rapid than it would with an instrument with thicker glass.

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