MODULE 2

THERMAL EQUILIBRIUM

Temperature is a measure of hotness & coldness.

Consider two blocks of copper, one hot &the other cold, each of which is in contact with
a mercury-in-glass thermometer. If these two blocks of copper are brought into thermal
communication, the electrical resistance of the hot block decreases with time & that of
the cold block increases with time. After a period of time, however, no further changes
in resistance are observed. Similarly, when the block are first brought in thermal
communication, the length of a side of the hot block decreases with time, but the length
of a side of the cold block increases with time. After a period of time, no further change
in length of either of the blocks is perceived. In addition, the mercury column of the
thermometer in the hot block drops at first & that in the cold block rises, but after a
period of time no further changes in height are observed.

ie. When two bodies are in thermal communication, if no change in any observable
property occurs, the two bodies have equality of temperature or they are in thermal
equilibrium.

So temperature of a system is a property that determines whether or not a system is in

thermal equilibrium with other systems.

ZEROTH LAW OF THERMODYNAMICS (R.H. FOWLER IN 1931)

The Zeroth law of thermodynamics states that when two bodies have equality of
temperature with a third body, they in turn have equality of temperature with each other.
OR

When a body A is in thermal equilibrium with a body B, & also separately with a body
C, then B and C will be in thermal equilibrium with each other

This law is the basis of temperature measurement.

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In order to obtain a quantitative measure of temperature a reference body is used, & a
certain physical characteristic of this body which changes with temperature is selected.
The changes in the selected characteristic may be taken as an indication of change in
temperature. The selected characteristic is called the thermometric property, and the
reference body which is used in the determination of temperature is called the
thermometer.

eg; A small amount of mercury in an evacuated capillary tube.

The extension of mercury in the tube is the thermometric property. Science that deals
with the temperature & its measurement is called thermometry.

There are five different kinds of thermometer, each with its own thermometric property.

Thermometer Thermometric Property

1) Constant volume gas thermometer - Pressure

2) Constant pressure gas thermometer - Volume

3) Electrical resistance thermometer - Resistance

4) Thermocouple - Thermal emf

5) Mercury-in-glass thermometer - Length

GAS THERMOMETERS

A small amount of gas (usually hydrogen or helium at low pressure) is enclosed in bulb
B. This bulb is in communication with one limb of mercury manometer M via a capillary
tube C. The other limb of the mercury manometer is open to the atmosphere & can be
moved vertically to adjust the mercury levels so that the mercury just touches the lip L of
the capillary. The pressure in the bulb is used as a thermometric property & is given by:

P = Po + ρMg Z where,

Po = atmospheric pressure

ρM = density of Hg.

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When the bulb is brought in contact with the system whose temperature is to be
measured, the bulb, in course of time, comes in thermal equilibrium with the system. The
gas in the bulb expands, on being heated, pushing the mercury downward. The flexible
limb of the manometer is then adjusted so that the mercury again touches the lip L. The
difference in mercury level Z is recorded & the pressure P of the gas is estimated. Since
the volume of the trapped gas is constant, form the ideal gas equation:

T = (V/ R) P

CONSTANT PRESSURE GAS THERMOMETER

In this the mercury levels have to be adjusted to keep Z constant, and the volume of gas
V, which would vary with the temperature of the system, becomes the thermometric
property.

T = (P/R) V

ie; the temperature increase is proportional to the observed volume increase.

ELECTRICAL RESISTANCE THERMOMETER (Sceimen 1871)

It is also known as ‘Platinum Resistance Thermometer’. It works on the principle of

change in resistance of the thermometric substance (platinum) with temperature. Thus
resistance is the thermometric property used in these thermometers. It consists of a pure
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platinum wire wound in a double spiral on a mica plate. The change of resistance of this
unit can be measured by the principle of wheat stone bridge. The resistance of wire can
be mathematically related as

Rt = Ro (1 + at+ bt2)

Where Ro is the resistance of the platinum wire when it is surrounded by molten ice & a
& b are constants.

THERMO ELECTRIC THERMOMETER (THERMO COUPLE)

Thermo electric thermometer works on the principle of Seeback effect. Seeback effect
says that a current flows or emf is produced in a circuit of two dissimilar metals having
one junction as hot while other as cold junction. Current produced in this way is called
thermo electric current while the emf produced is called thermo emf. Measurement of
temperature is being done by knowing the emf produced which is the thermometric
property.

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Every time a body has equality of temperature with the thermometer; we can say that the
body has the temperature we read on the thermometer. The problem remains how to
relate temperatures that we might read on different mercury thermometer or obtain from
different temperature measuring devices, such as thermocouples & resistance
thermometers. This observation suggests the need for a standard scale for temperature
measurement (or standard reference points).

TEMPERATURE SCALES

Two scales are commonly used for measuring temperature, namely the Fahrenheit (after
Gabriel Fahrenheit) and the Celsius. The Celsius scale was formerly called the
centigrade scale but is now designated the Celsius (after Anders Celsius).

Until 1954, both of these scales were based on two fixed, easily duplicated points- the
ice point & the steam point.

The temperature of the ice point is defined as the temperature of a mixture of ice &
water that is in equilibrium with saturated air at a pressure of 1 atm.

The temperature of the steam point is the temperature of water & steam, which are in
equilibrium at a pressure of 1 atm.

 (X1)/ (X) = X1/X …………. (1)

 (X2)/ (X) = X2/X ………..... (2)

{ (X1) -  (X2)}/ (X) = (X1 - X2)/X

ie; (X) = [{ (X1) -  (X2)}/ (X1 - X2)].X

On the Fahrenheit scale ice point is assigned as 32 and steam point as 212. On the
Celsius scale the values are 0 and 100 respectively.
0
C = (0F - 32)/1.8

In 1954, the Celsius scale was redefined in terms of a single point, which is the triple
point of water, & the magnitude of degree is defined in terms of the Ideal gas

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temperature scale. The triple point of water is assigned the value 0.010c & the steam
point was experimentally found as 1000 C. Thus there is essential agreement between old
& new temperature scales.

Triple point of water is the state in which the solid, liquid & vapour phases of water exist
together in equilibrium.

For ideal gas, PV = RT

P1/ T1 = P2/ T2

T2 = T1 (P2/ P1)

ie. T2 = 273.16 (P2/ Ptp)

Triple point temperature = 0.010C = 273.16 K

Ptp = Pressure at triple point.

Why an ideal Gas Temperature Scale?

It is known that all materials do not change their thermometric properties linearly with
temperature. Therefore different thermometers made of different thermometric material
show different values of the temperature of a body except at the points at which they are
calibrated. Hence to have reliable and reproducible values of temperature, it is necessary
to devise a temperature scale which does not depend on the nature of thermometric
material. However the smallest variation is observed among different gas thermometers.
So a gas is chosen as standard thermometer substance. This is the basis of establishment
of ideal gas temperature scale.

IDEAL GAS OR PERFECT GAS TEMPERATURE SCALE

This scale is based on the observation that as the presence of a gas approaches zero, its
equation of state approaches that of an ideal gas.

PV = RT

ie. P/T = const (for constant volume gas thermo meter).

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P/ T = Ptp / Ttp

T = Ttp (P/ Ptp)

Consider a constant volume gas thermometer containing an amount of gas such that
when the bulb is surrounded by water at its triple point, the pressure be Pt &is 1000 mm
of Hg. Keeping the volume constant, the following procedure is followed.

a) Surround the bulb with steam condensing at 1 atm, determine the pressure P 2

PV = RT

V = a const here, P = Po + ρMgz

Hence, P1/ T1 = P2 / T2

T2 = T1 (P2/ P1)

T2 = 273.16 (P2/1000)

T1 = Temperature at triple point = 0.010c = 273.16 K

P1 = Pt = 1000 mm of Hg

b) Remove some gas from the bulb so that when it is surrounded by water at its triple
point, the pressure Pt is 500 mm of Hg. Determine P3 & temperature T3 for steam
condensing at 1 atm.

T3 =273.16 (P3/500)

c) Continue reducing the amount of gas in the bulb so that P 2 & P (pressure for steam
condensing at 1 atm) have smaller & smaller values.

eg. Pt having 250 mm Hg, 100 mm Hg & so on. At each value of Pt calculate the
corresponding temperature.

d) Plot T Vs Pt and explorate the curve to the axis where Pt = 0. Read from the graph.

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Let there be gas B instead of A in the bulb. The operation of constant volume gas
thermometer will give another set of values. However when extrapolated to zero
pressure, the T graph will intersect the ordinate giving the same value as for gas A. ie
difference curves might result from different gases , but they would all indicate the same
temperature at zero pressure. This temperature is refereed as ideal gas temperature for
steam point.

By measuring the pressures Ptp & Pi (Pressure at triple point and pressure at ice point
respectively), the value of ice point temperature;

From T Vs Ptp graph

Thus the value of temperature at various fixed points can be obtained. The empirical
scale thus developed is referred as Ideal Gas Temperature Scale.

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Ideal Gas Temperature Scale is not a thermodynamic temperature scale since it cannot
be used at very low temperatures (due to condensation) and at very high temperatures
(due to dissociation & ionization). However ideal gas temperature is identical to the
thermodynamic temperature in the temperature range in which the gas thermometer can
be used.

Q) A thermocouple in which the voltage output V = At + Bt 2 where t is the temperature

in 0C. It reads zero at ice point and 15 mV at steam point. If finally it reads 10 mV,
calculate the temperature.

Ans.

t = Vt (ts – ti)/ (Vs – Vi)

= {10 (100 – 0)}/ (15- 0) = 66.670C

Q) A thermocouple with test junction at t0C on gas thermometer scale & reference
junction at ice point gives the imp as, e = 0.20t – 5 x 10-4 t2mV.

The milli voltmeter is calibrated at ice & steam points. What will be the reading on this
thermometer where the gas thermometer reads 700C.? Also determine the % variation in
temperature with respect to gas thermometer.

Ans.

e = 0.20t – 5 x 10 – 4 t2 mV

At ice point, when t = 00C, e = 0

At steam point, when t = 1000 C,

e = 0.20 x100 –5 x 10 – 4(1002) = 15 mV

When t = 700 C

e = 0.20 x70 –5 x 10 – 4(702) = 11.55 mV

When the gas thermometer reads 700C the thermocouple will read,

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t = {et (ts - ti)}/ (es - e1)

t = {11.55 (100)}/ 15 = 770C

% variation with respect to gas thermometer, = (77 – 70)/70 x 100 =10%

Q. A temperature scale of certain thermometer is given by relation t = a lnp + b,

When a & b are constants & p is the thermometric property of the fluid in the
thermometer. If at the ice point & steam point the thermometric properties are found to
be 1.5 & 7.5 respectively, what will be the temperature corresponding to the
thermometric properly of 3.5 on Celsius scale.

Ans.

t = a lnp + b ……… (1)

On Celsius scale, ice point = 00 C

Steam point = 1000 C

Substituting in (1),

0 = a ln 1.5 + b

100 = a ln 7.5 + b

ie, 0 = a x 0.4054 + b ……(2)

100 = a x 2.015 + b …… (3)

Substracting (2) from (3),

100 = 1.61 a

ie, a = 62.112

Substituting for a in (2),

b = - 0. 4054 x 62.112 = -25.18

When p = 3.5, the value of temperature is given by

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t = 62.112 ln (3.5) – 25.18 = 52.630C

Q. Determine the human body temperature in degree Celsius of the temperature in

Fahrenheit is 96.80 F
0
C = (0F – 32)/ 1.8

= (96.8 – 32)/ 1.8 = 360C

Q. On some scale of temperature, 00C is equivalent to 100 0B & 1000C is equivalent to

3000B. Determine the temperature in 0C corresponding to 2000B.

Ans.

Let the relation between 0B & 0C be

0
B = a 0C + b

100 = a x 0 + b ………. (1)

ie, b = 100

Again, 300 = a x 100 + b …….. (2)

ie 300 = a x 100 + 100

a = (300 – 100)/ 100 = 2

For 2000 B;

200 = 2 x 0C + 100
0
C = (200 -100)/ 2 = 500C

Q. Consider an alcohol & a mercury thermometer that read exactly 0 0C at the ice point &
1000C at the steam point. The distance between the two points is divided into 100 equal
parts in both the thermometers. Do you think these thermometers will give exactly the
same reading at a temperature of say 60 0C. Explain.

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Q. Consider two closed systems A & B. System A contains 3000 kJ of thermal energy at
200C whereas system B contains 200 kJ of thermal energy at 50 0C. Now the systems are
brought into contact with each other. Determine the direction of any heat transfer
between the two systems.

WORK & HEAT

Energy can cross the boundary of a closed system in two distinct forms: heat & work.
These may be called energy interaction & these bring about changes in the properties of
the system.

WORK

The energy interaction that is not caused by a temperature difference between a system
& surroundings is work.

Work is usually defined as a force F acting through a displacement x, the displacement

being in the direction of the force. That is,

W = 21 F dx

The definition of work with the concept of systems, properties & processes is as follows:

Work is done by a system if the sole effect on the surroundings could be the raising of a
weight.

Notice that the raising of a weight is in effect force acting through a distance.

Consider a system of battery & motor driving a fan. Does work cross the boundary of the
system? To answer the question using the definition of work, replace the fan with the
pulley & weight arrangement. As the motor turns, the weight is raised, & the sole effect
external to the system is the raising of a weight. Thus we conclude that work is crossing
the boundary of the system since the sloe effect external to the system could be the
raising of a weight.

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eg: A rising piston, a rotating shaft, & an electric wire crossing the system boundaries
are all associated with work interactions.

UNIT OF WORK

Work done by a system, such as that done by a gas expanding against a piston is positive
and work done on a system, such as that done by a piston compressing a gas, is negative.
Thus positive work means that energy leaves the system, & negative work means that
energy is added to the system.

Unit of work is called joule (J).

I J = I Nm

The rate of doing work is called power

P = WD/t = J/s or Nm = Watts =

The value of work depends on the nature of interactions taking place during the process
between the system & surrounding Different types of work are:

1. PdV work or displacement work.

2. Electrical work = W = 21 E I dτ

dτ = time ; P = - E I

E = voltage

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3. Shaft work. = W = 21 Tdө

T = Torque

dө = angular displacement

P = Tω, ω = angular velocity

4. Flow work, W = Pνm

5. Paddle wheel work or stirring work etc.

W = 21 mg dz = 21 T dө

T = torque transmitted by shaft rotating do angle.

M = mass lowered through distance dz

6. Work done in stretching wire = -21 τ dL, where τ = tension

7. WD in changing area of surface form = 21 dA, where  = surface tension N/M

PdV work or DISPLACEMENT WORK OR WORK DONE AT THE MOVING

BOUNDARY OF A QUASI EQUILIRIUM PROCESS

Consider a piston cylinder arrangement with a gas. Let one of the small weights over the
pistons is removed which causes the piston to move upward through a distance dL.

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We can consider this as a quasi-equilibrium process & calculate the amount of work
done by the system during the process. The total force on the piston is PA, where P is the
pressure of the gas & A is the area of the piston.

Work w = PA dL

But AdL = dV, the change in volume of gas, w = PdV

The total work in expanding the gas from state 1 to state 2 can be obtained by integrating
the above expression with the limits 1 to 2.
2
1 dw = 21 P dV = P [V ]21

= P (V2 - V1) (+ve)

In the case of compression work,

W = p 21 dV (-ve)

REQUIREMENT FOR A WORK INTERACTION BETWEEN SYSTEM &

SURROUNDINGS

1. There must be force acting on the boundary.

2. The boundary must move.

* Presence of forces on the boundary without any displacement of the boundary

does no work.

* Displacement of the boundary without any force to oppose does no work.

eg: expansion of gas into an evacuated space does no work.

FREE EXPANSION WITH NO WORK TRANSFER

Consider a gas separated from the vacuum by a membrane. Let the membrane rupture
and the gas fills the entire volume. Neglecting the work associated with the rupturing of
the membrane.

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a) If we consider the gas & the vacuum as a system;

No work is done because no work can be identified at the system boundary or no work
crosses the system boundary.

b) If we consider the gas alone as a system;

We do have a change of volume & we might be tempted to calculate the work from the
integeral 21 PdV. However, this is not a quasi-equilibrium process, & therefore the work
cannot be calculated from this relation. Because there is no resistance at the boundary as
the volume increases, we conclude that for this system no work is done in this process of
filling the vacuum.

NET WORKDONE BY A SYSTEM

W total = W displacement + W shaft + Stirring + W electrical + --------

PATH FUNCTION & POINT FUNCTION

Consider various quasi – equilibrium processes between to given states 1 & 2.

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Thermodynamic properties are point functions & that for a given point on the curves, the
state is fixed, & there is a definite value of each property corresponding to this point.
The Change in thermodynamic property of a system in a change of state is independent
of the path of the system following during the change of state. Instead the values depend
only on the initial & final states of the system. The differential of point functions is exact
or perfect differential.

Here volume in state 1 & 2 depends only on the initial & final states.
v2
v1 dV = V2 – V1

Since the area underneath each curve represents the work for each process, it is evident
that the amount of work done during each process not only is a function of the end states
of the process, but depends on the path that is followed in going from one state to
another. For this reason work is called a path function. The differentials of path function
are inexact differentials.

ie. 21 dw  W2 – W1

but 2
1 dw = W1-2 or W2 or , W2A to be precise.

HEAT

Heat is defined as the form of energy that is transferred across the boundary of the
system at a given temperature to another (or the surroundings) at lower temperature by
virtue of the temperature difference between the two systems.

A body never contains heat; rather heat can be identified only as it crosses the boundary.
Thus heat is a transient phenomenon.

Thus transfer of energy to or from a system due to temperature difference is heat, all the
rest being work. As it is energy, the unit of heat is Joule.

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Heat transferred to a system is considered positive, and heat transferred from a system is
negative. The symbol ‘Q’ represents heat. A process in which there is no heat transfer, ie
Q = 0, is called on adiabatic process.

Like work, heat is also a path function. ie, the amount of heat transferred when a system
undergoes a change from state 1 to state 2 depends on the path that the system follows
during the change of state.

ie. 21 dQ = 1Q2

Q = dQ/dt, ie rate of heat transfer.

MODES OF HEAT TRANSFER

1) Conduction :- transfer of heat between particles of two system at different

temperature in direct contact with each other due to molecular collision without any
appreciable macroscopic displacement of molecules

By Fourier’s Law Heat transfer rate, Q = - KA dT/ dx Watts

K = conductivity = Temperature gradient.

A = Area

eg. Glass of liquid with air around it

2) Convection: - mode of heat transfer when a media is flowing.

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eg. Wind blowing over a building, flow through heat exchangers, etc.

By Newton’s law of cooling, Q = Ah  T

h = heat transfer coefficient

3) Radiation: - transmits energy as electromagnetic waves in space. The transfer can

happen in empty space & does not require any matter, but the emission (generation) of
the radiation & the absorption does require substance to be present.

The maximum rate of radiation that can be emitted from a surface at an absolute
temperature Ts, is given by Stefan – Boltzman law as.

Qmax =Ats4  = Stefan Boltzman const.

The idealized surface that emits radiation at this maximum rate is called a black body.
Radiation emitted by a real surface is less than the radiation emitted by a black body at
the same temperature and is given by

Q = E  ATs4

E = emissivity of surface.

Real surface O< ε < 1

Black body ε = 1

Absorptivity α, which is the fraction of the radiation energy incident on a surface that is
absorbed by the surface red surface 0    1

 b = 1 as black body is a perfect absorber.

Kirchoff’s law of radiation: - Emissivity & absorptivity of a surface are equal at the
same temperature & wave length.

COMPARISON OF HEAT & WORK

1. Heat & work are both transient phenomena. Systems never possess heat or work,
but either or both cross the system boundary when a system undergoes a change of state.

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2. Both heat & work are boundary phenomena. Both are observed only at the
boundaries of the system, & both represent energy crossing the boundary of the system.

3. Both heat & work transfers are path functions and inexact differentials.

4. Heat transfer & work transfer are the energy interactions by which a closed
system & its surroundings interacts each other.

5. The same effect in a closed system can be brought about either by heat transfer or
by work transfer.

6. Heat transfer is the energy interaction due to temperature difference only. All
other energy interactions are work transfer.

FIRST LAW OF THERMODYNAMICS FOR A CLOSED SYSTEM

UNDERGOING A CYCLE

The first law of thermodynamics states that, for a closed system undergoing a cycle, the
cyclic integral of the heat is proportional to the cyclic integral of work.

The transfer of heat & the performance of work may both cause the same effect in a
system. Heat & work are different forms of the same entity, called energy, which is
conserved. Energy which enters a system as heat may leave the system as work, or
energy which enters the system as work may leave as heat.

Consider the gas in a container as shown. Let this system go through a cycle that is made
up of two processes. In the first process work is done on the system by the paddle that
turns as the weight is lowered. Let the system then return to its initial state by
transferring heat from the system until the cycle has been completed.

When the amounts of work & heat are compared, it is found that they are always
proportional. This is known as the first law of thermodynamics, which is in the equation
form, is:

J dQ =  dw

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The symbol dw , which is called the cyclic integral of the heat transfer, represents the
net heat transfer during the cycle, and  dw, the cyclic integral of the work, represents
the net work during the cycle. Here, J is a proportionality factor that depends on the units
of work & heat, (which is Joule’s equivalent)

In SI system of units, both heat & work are measured in joule. Therefore Joule’s
equivalent is unity.

ie. J = 1Nm/J

 dQ =  dw

This is the basic statement of first law of thermodynamics.

This law is often called the law of conservation of energy. It was J.P Joule who first
established that heat is a form of energy, & thus laid the foundation of the first law of
thermodynamics.

FIRST LAW FOR A CLOSED SYSTEM UNDERGOING A CHANGE OF STATE

The first law of thermodynamic for a closed system undergoing a change of state states
that the net energy transfer will be stored or accumulated within the system. If Q is the
amount of heat transferred to the system & W is the amount of work transferred from the
system during the process, the net energy transfer

(Q – W) will be stored in the system. Energy storage is neither heat nor work.

ie. Q – W = E

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Where Q, W & E are expressed in Joules. Energy may be stored by a system in
different modes.

If there are more energy transfer quantities involved in the process as shown;

The first law gives:

(Q2 + Q3 – Q1) = E + (W2+W3-W1 –W4)

Energy is thus conserved in the operation. The above equation may also be considered as
the definition of energy. The definition does not give an absolute value of energy E, but
only the change of energy E for the process.

eg. 1. Consider a process that involves heat transfer but no work transfer as in the case
of baking a potato. That is if 5 kJ of heat is transferred to the potato the energy increase
of the potato will also be 5 kJ.

1. Consider a process that involves work transfer but no heat transfer as in the case
of an electric heater in an adiabatic room. The electrical WD on the system is equal to
the increase in energy of the system.

2. Consider a system that involve both heat & work interaction. If a system gains 12
kJ of heat during a process while 6 kJ of work is done on it the increase in energy of the
system during that process is 18 kJ.

ie, the change in energy of a system during a process is simply equal to the net energy
transfer to (or from) the system.

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23
CONCEPT OF ENERGY

Consider a system which changes its state from. State 1 to state 2 by following the path
A, & returns from state 2 to state 1 by following the path B & C. So the system
undergoes a cycle.

Applying first law for path A & B separately,

QA = EA + WA ………………… (1)

QB = EB + WB ………………… (2)

The process A & B together constitutes a cycle, then;

 dQ = dw

QA+ QB = WA +WB

ie, QA – WA = WB - QB

From (1) & (2) = ie EA = - EB ………………. (3)

Similarly considering the process A & C constituting a cycle we get.

EA = - EC ……………… (4)

From (3) & (4), we get

EB = - EC = EA

Therefore, it is seen that the change in energy between two states of a system is the
same, whatever path the system may follow in undergoing that change of state. If some

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arbitrary value of energy is assigned to state 2, the value of energy at state 1 is fixed
independent of the path the system follow. Therefore, energy has a definite value for
every state of the system. Hence it is a point function & thus a property of the system.

The physical significance of the property E is that it represents all the energy of the
system in the given state. This energy might be present in a variety of forms, such as the
KE or PE of the system as a whole energy associated with motion & position of the
molecules, energy associated with the structure of atom, chemical energy present in a
storage battery, energy in a changed condenser or in any of a number of other forms.

In thermodynamics, we will consider KE & PE & all other forms taken together as
internal energy of the system.

E = internal energy + KE + PE

ie, E = U + KE + PE

If we neglect the position, motion, effect of gravity, & electricity we get internal energy
only.

ie. E = U, where U is internal energy stored in the molecular structure of the system.

ie. Q – W = U

Energy of an isolated system is constant since there is no work or heat transfer access the
boundary, ie E = 0, for isolated system.

ENTHALPY

Consider a system undergoing a quasi- equilibrium constant pressure process. Applying

first law

1Q2 = U2 – U1 + 1W2

The work can be calculated from 1W2 = 21 PdV

Since pressure is constant,

1W2 = 21 dV = P (V2 –V1)

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 1Q2 = U2 – U1 + P2V2 – P1V1

ie, 1Q2 = (U2 + P2V2) – (U1 + P1V1)

ie, heat transfer for constant pressure is can be shown as the change in quantity U + PV
between initial & find states.

Since U, P & V are thermodynamic properties; their combination of (U +PV) has the
same characteristic. ie (U + PV) is also a thermodynamic property & is termed as
enthalpy.

ie. Enthalpy is a thermodynamic property & will have definite value at state points with
respect to some reference point.

For steam stables, the internal energy of saturated liquid at 0.010C is the reference state
& is taken as zero. Enthalpy is taken as zero.

For refrigerants, such as ammonia & chlorofluoro carbons & R -12 & R -22, the
reference state is taken as saturated liquid at -400C. The enthalpy is taken zero for this
reference point.

Specific internal energy, u = U/m

Specific enthalpy, h = H/m

SPECIFIC HEATS

1) SPECIFIC HEAT AT CONSTANT VOLUME (CV)

It is the amount of heat added or removed per degree change in temperature when the
system is kept at constant volume. It is denoted as CV.

By first law, 1Q2 - 1W2 = U

For constant volume process, dV = 0

26
WD = PdV= 0

ie, 1Q2 = U

Or, U = mCV T

2) SPECIFIC HEAT AT CONSTANT PRESSURE (Cp)

It is the amount of heat added or removed per degree change in temperature when the
system is kept under constant pressure. It is denoted by Cp.

For a constant pressure process; 1Q2 = H

H = mCp T

RELATIONSHIP FOR Cp, Cv, R

Enthalpy, H = U + PV

For an ideal gas, PV = mRT

H = U + mRT

H = U + mR T …………. (1)

But H = mCp T and U = mCVT

Substituting in (1) we get,

27
mCp T = mCVT + mR T

ie, Cp = Cv + R

Cp – Cv = R ……………. (2)

Dividing by CV,

{Cp/ CV}- 1 = R/CV

Cp/ CV = γ

 γ – 1 = R/CV

 CV = R/ (γ – 1)

Substituting for CV in equation (2),

Q. In an internal combustine engine, during the compression stroke the heat rejected to
the cooling water is 50kJ/kg and the work input is 100 kJ/kg. Calculate the change in
internal energy of the working fluid stating whether it is a gain or loss.

Ans. Q = -50 kJ/kg, W = -100 kJ/kg, ∆u =?

Q = ∆u + W

-50 = ∆u – 100

∆U = -50 + 100 = 50 kJ/kg

28
Q. In an air motor cylinder the compressed air has an internal energy of 450 kJ/kg at the
beginning of the expansion and an internal energy of 220 kJ/kg after expansion. If the
work done by the air during the expansion is 120 kJ/kg, calculate the heat flow to and
from the cylinder.

Ans.

U1 = 450 kJ/kg, U2 = 220 kJ/kg, W = 120 kJ/kg

Q = (220 - 450) +120 = -110 kJ/kg

ie, heat is rejected from the air.

Q. 0.3 Kg of nitrogen gas at 100 kPa & 400C is contained in a cylinder. The piston is
moved compressing nitrogen until the pressure becomes 1 MPa & temperature becomes
1600C. The work done during the process is 30 kJ. Calculate the heat transferred from
nitrogen to the surroundings. CV for N2 = 0.75 kJ/kg K.

Ans.

m = 0.3 kg, P1 = 100 kPa, P2 = 1 MPa, T1 = 400C = 313 K, T2 = 600C = 433K

W = -30 kJ (compression), Q =?

Q = ∆U + W

∆U = ∆m CVT = 0.3 x 0.75(433 - 313) = 27 kJ

∆Q = ∆U + W = 27 – 30 = -3 kJ

ie, heat is rejected during the process.

Q. When a stationary mass of gas was compressed without friction at constant pressure
its initial state of 0.4 m3 and 0.105 MPa was found to change to final state of 0.20 m3 and
0.105 MPa. There was a transfer of 42.5 kJ of heat fro m the gas during the process.
How much did the internal energy of the gas change?

29
Ans.

V1 = 0.4m3, P1 = 0.105 MPa, V2 = 0.2m3, P2 = 0.105 MPa, Q = -42.5 kJ

∆U =?

Q = W + ∆U

W = PdV

ie, W = 0.105 x 103 (0.2 – 0.4) = -21 kJ

∆U = Q – W = - 42.5 – (-21) = -21.5 kJ

ie, there is a decrease in internal energy.

Q. A cylinder containing the air comprises the system. Cycle is completed as follows:

i) 82,000 Nm of work is done by the piston on the air during compression stroke & 45 kJ
of heat is rejected to the surroundings.

ii) During expansion stroke 100000 Nm of work is done by the air on the piston.

Calculate the quantity of heat added to the system

Ans.

Compression stroke

Work done = -82000 Nm = -82 kJ

Q = -45 kJ

∆U = Q – W = -45 – (-82) = 37 kJ

Expansion stroke

W = 1000000 Nm = 100 kJ

∆U = -37 kJ

30
Q = U + W = -37 + 100 = 63 kJ

The total heat added to the system.

Q. A rigid tank contains a hot fluid that is cooled while being stirred by a paddle wheel.
Initially the internal energy of the fluid is 800 kJ. During the cooling process, the fluid
loses 500 kJ of heat, & the paddle wheel does 100 kJ of work on the fluid. Determine the
final energy of the fluid.

Ans.

U1 = 800 kJ, Q = -500 kJ, W = -100 kJ

U2 =?

Q = ∆U + W

-500 = (U2 - 800) + -100

U2 – 800 = -500 - (-100) = - 400

U2 = -400 + 800 = 400 kJ

Q. The properties of a certain fluid are related as follows. u = 196+0.718t, Pv = 0.287 (t

+ 273), where u is the specific internal energy (kJ/kg), t in 0C. P is pressure (kN/m2) and
v is the specific volume in m3/kg. Find CP & CV for the fluid.

Ans.

u = 196 + 0.718 t, Pv = 0.287 (t + 273)

du/dt = 0.718

du = CVdt

Therefore, CV = du/dt = 0.718 kJ/kg

31
h = u + Pv

u = 196 + 0.718 t ……………….. (1)

Pv = 78.351 + 0.287 t ………….. (2)

(1) + (2), h = 274.351 + 1.005 t

Therefore, dh/dt = 1.005

dh = Cp dT

Therefore, CP = dh/dt = 1.005 kJ/kg

Q. A fluid is contained in a cylinder with a piston so that the pressure in the fluid is a
linear function of the volume P = a + bv. The internal energy of the fluid is given by U
= 42+ 3.6 PV.

Where, U is the kJ, P in kPa, & V in m3. If the fluid changes from an initial state of 190
kPa, 0.035m3 to a final state of 420 kPa, 0.07m3, with no work other than that done on
the piston, find the direction & magnitude of work & heat transfer.

Ans

P = a + bv, P1 = 190 kPa, P2 = 420 kPa, V1 = 0.035m3, V2 = 0.07m3

U = 42+3.6 PV

U = U2 – U1 = (42+3.6 P2V2) - (42+3.6 P1V1)

= 36 (P2V2 - P1V1)

= 3.6 x 103 (4.2 x 0.07 – 1.9 x 0.035) kJ = 81.9 kJ

P = a + bv

190 = a + b x 0.035 ………….. (1)

420 = a + b x 0.07 ………….. (2)

(1) - (2)  230 = 0.035 b

32
Therefore, b = 230/0.035 = 6571 kN/m5

a = - 40 kN/m2

W = ∫ pdV = ∫ (a+bV) dV

W = a (V2 – V1) + b {(V22 – V12)/2}

ie, W = (V2 – V1) [a + b/2 (V1 + V2)]

ie, W = (0.074 – 0.035) [- 40 kN/m2 + 6571 kN/m2 (0.035 +0.07)] = 10.67 kJ

Q = ∆U + W

ie, Q = 81.9 + 10.67 = 92.57 kJ

Q. Gas from a bottle of compressed helium is used to inflate an inelastic flexible balloon,
originally folded completely flat to a volume of 0.5m3. If the barometer reads 760 mm
Hg, what is the amount of work done upon the atmosphere by the balloon?

Ans.

V1 of balloon = 0, V2 of balloon = 0.5m3

P = 760mm of Hg = 1.01325 x 105 N/m2 = 101.325 kN/m2

Wd = ∫ pdv + ∫ pdv
balloon bottle

= P (V2 – V1) + (P x 0) = 101.325 kN/m2 x 0.5 m3 = 50.66 kJ

Work is +ve as work is done by the balloon.

Q. When the value of an evacuated bottle is opened, atmospheric air rushes into it. If the
atmospheric pressure is 101.325 kPa, and 0.6m3 of air (measured at atmospheric
condition) enter into the bottle. Calculate the work done by air.

33
Ans.

P = 101.325 kPa, V1 of air in bottle = 0, V2 of air in bottle = 0.6m2

Wd = ∫ pdV + ∫ pdV
Bottle Free air

Wd = 0 + 101.325 (0.6 - 0) = 60.8 kJ

Since the free air boundary is contracting, the work done by the system is negative, ie,
Wd = - 60.8 kJ

If the temperature and pressure becomes atmospheric after filling, determine the amount
of heat transfer.

W = - 60.8 kJ

Heat transfer, Q = 60.8 kJ

Q. A piston and cylinder machine containing a fluid system has a stirring device in the
cylinder. The piston is frictionless and it is held down against the fluid due to
atmospheric pressure of 101.325 kPa. The stirring device is toned 10,000 revolutions
with an average torque against the fluid of 1.275 MN. Meanwhile the piston of 0.6m
diameter moves out 0.8m. Find the net work transfer for the system.

Ans.

P = 101.325 kPa, N = 10,000, d = 0.6m, T = 1.275 mN, L = 0.8m

Work done by the stirring device up on the system = W1 = 2  TN

W1 = 2 x 1.275 x10, 000 Nm = 80 kJ

W1 = -80 kJ as work done is on the system.

Work done by the piston on the surrounding, = W2 = (PA) L

W2 = 101.325 x /4 0.62 x 0.8 = 2.9 kJ

34
W = W1 + W2 = - 80 + 22.9 = - 57.1 kJ

Q. A piston and cylinder machine contains a fluid system which passes through a
complete cycle of 4 processes. During a cycle, the sum of all heat transfers is –170kJ.
The system completes 100 cycles per min. Complete the following table showing the
method for each item, and compute the net rate of work output in kW.

Process Q kg/min. W (kJ/min) ∆E (kJ/min)

a-b 0 2170 -

b-c 21,000 0 -

c-d -2,100 - -36,600

d-a - - -

Ans.

a-b

Q = ∆E + W

0 = ∆E + 2170

∆E = -2170 kJ/min

b- c

Q = ∆E + W

21,000 = ∆E + 0

∆ E = 21,000 kJ/min

c-d

Q = ∆E + W

35
-2100 = -36,600 + W

W = 34,500 kJ/min

d- a

 Q = -170 kJ
cycle
The system completes 100 cycles / min.

Qab + Qbc + Qcd + Qda = -17,000 kJ/min.

0 + 21,000 – 2100 + Qda = -17,000

Qda = -35,900 kJ/min.

Now  dE = 0, since cyclic integral of any property is zero.

∆Eab + ∆E bc + ∆ E cd + ∆E da = 0

-21, 70 + 21,000 – 36,000 + ∆E da = 0

∆Eda = 17,770 kJ/min

Wda = Qda – ∆Eda = -35,900- 17,770 = -53,670 kJ/min.

Since  Q = W
cycle cycle

Rate of work output = -17,000 kJ/min = -283.3 kN

The first law states the general principle of the conservation of energy. Energy is neither
created nor destroyed, but only gets transformed from one form to another. There can be
no machine which would continuously supply mechanical work without some other form
of energy disappearing simultaneously. Such a fictitious machine is called a perpetual
motion machine of the first kind, or in brief, PMMI. A PMMI is thus impossible.

The converse of the above statement is also true, i.e. there can be no machine which
would continuously consume work without some other form of energy appearing
simultaneously.

36
FIRST LAW OF THERMODYNAMICS APPLIED TO OPEN SYSTEMS

A large number of engineering devices such as turbines, compressors, and nozzles operate for
long periods of time under the same conditions once the transient start-up period is completed and
steady operation is established, and are classified as steady-flow devices. Processes involving
such devices can be represented reasonably well by a somewhat idealized process, called the
steady-flow process. That is, the fluid properties can change from point to point within the
control volume, but at any point, they remain constant during the entire process.

(Steady means no change with time.)

Thus, the volume V, the mass m, and the total energy content E of the control volume remain
constant and the total mass or energy entering the control volume must be equal to the total mass
or energy leaving it (since mcv = constant and Ecv = constant).

Consider an open system having an inlet at section 1- 1 and outlet at section 2 –2.

The cross sectional area, pressure, specific volume, mass flow rate at 1 –1 & 2 –2 are;

1-1  A1, P1, v1, m1

2 –2  A2, P2, v2, m2

The fluid flowing across the control surface enters & leaves with an amount of energy
per unit mass.

e1 = u1 + ½ C12 + gz1

37
e2 = u2 + ½ C22 + gz2 for 1 –1 & 2 –2 respectively.

Again as the amount of mass flows in there is a pressure at its back surface so that it is
being pushed by the mass behind it, which is the surroundings. This is the work flowing
in similarly the fluid flowing out must push the surrounding fluid ahead of it doing work
on it, which work is leaving the open system.

Flow work = Force x velocity

=  PdA x velocity (AC =V)

= PV = Pvm

 Flow work in = P1v1m1

Flow work out = P2v2 m2

The total energy associated with the flow of mass = [Stored energy + flow energy]

(e + Pv) m = [(u + Pv) + ½ C2 + gz] m

ie, (e + Pv)m = (h + ½ C2 + gz)m

ie, m1(e1+P1v1) for 1- 1

m2 (e2+P2v2) for 2- 2

Let the open system is also having heat & work interactions, Q & W

The change in energy due to heat & work interaction = Q –W.

38
The fundamental law states that we cannot create or destroy energy such that the change
of energy must be caused by energy into or out of the open system (control of volume).

So the total change in energy for the system

ΔEcv = [Q – W] + [m1 (e1 + p1 v1) - m2 (e2+P2v2)]

ie, ΔEcv = Q – W + m1(h1 + ½ C12 + gz1)- m2(h2+½ C22 + gz2)

During a steady- flow process, the total energy content of the control volume is constant
ie change in energy ΔEcv = 0, then

Q + m1 (h1 + ½ C12 + gz1) = W + m2 (h2+½ C22 + gz2)

ie, the amount o energy entering a control volume in all forms (by heat, work & mass)
must be equal to the amount of energy leaving it. There is no accumulation of mass or
energy within the control volume & the properties of any location within the control
volume will not change with time.

By equation of continuity, mi = mе

ie, A1C1/ v1 = A2C2/v2

For a system of perfectly insulated type, Q = 0

(h1 + C12/2 + gz1) = W + (h2+ C22/2 + gz2)

b) For any system having more than one inlets, outlets and energy interactions.

Net heat added, Q = Q1 – Q2 +Q3

Net work done, W = W1 +W2

Applying SFEE,

39
Q + m1(h1+C12/2+gz1) + m2(h2+C22/2+gz2) = W +m3(h3+C32/2+gz3) + m4(h4+ C42/2+gz4)

FIRST LAW APPLIED TO ENGINEERING SYSTEMS

In applying the first law applied to different engineering systems, it is assumed that the
processes are of steady flow type.

TURBINE

It is a device which produces shaft work at the expense of the pressure of the working
fluid.

Q + (h1 + C12/2+ gz1) m1 = W + (h2+ C22/2+ gz2) m2

m1 = m2

KE & PE changes are negligible.

40
The expansion is assumed to be adiabatic ie; Q = 0.

mh1 = W + mh2

W = m (h1 – h2) = m Cp (T1 –T2)

ie. Work is done by the fluid at the expense of its enthalpy.

COMPRESSOR AND PUMP

In both compressor and pump the pressure of the fluid is increased by putting in shaft
work.

Q + m1 (h1 + C12/2 + gz1) = W + m2 (h2+ C22/2+ gz2)

PE = 0, Q = 0, m1 = m2, C1 is negligible

 mh1 = w + mh2 + C22/2

 W = m (h1 – h2) - C22/2

If C2 is also neglected

W = m (h1 – h2) = mCp (T1 –T2)

But W is negative as it is work input in this case.

41
HEAT EXCHANGER /CONDENSER

A heat exchanger is a device in which heat is transferred from one fluid to another.

Figure shows a steam condenser, where steam condenses outside the tubes & cooling
water flows through the tubes.

KE =0,  PE = 0, Q = 0, W=0

mch1++msh2 = mch3++msh4

ie. mc (h1- h3) = ms(h4-h2)

BOILER

Boiler is the device used for steam generation at const pressure. Heat is supplied
externally to the boiler for steam generation upon state of steam desired.

42
W = 0, KE = 0,  PE = 0, m1 = m2

Q + mh1 = mh2

Q = m (h2 – h1) = mCp(T2 –T1)

NOZZLE & DIFFUSER

A nozzle is a device which increases the velocity or KE of a fluid at the expense of its
pressure drop, whereas a diffuser increases the pressure of a fluid at the expense of its
KE.

Q = 0, W = 0, PE = 0, m1 = m2

 m (h1 + C12/2) = m (h2+ C22/2)

Compared to exit velocity, inlet velocity is negligible,

h1 = (h2+ C22/2)

ie. h1 = h2+ C22/2

or, C2 =  2(h1 – h2) m/s

Where h1 – h2 is in J/kg

43
THROTTLING PROCESS

When a fluid flows through a constricted passage, like a partially opened valve, an
orifice, or a porous plug, there is an appreciable drop in pressure, & the flow is said to be
throttled.

Q = 0, W = 0, PE = 0, m1 = m2

ie. (h1 + C12/2) = m (h2+ C22/2)

ie. h1 + C12/2 = h2 + C22/2

Often the pipe velocities in throttling are so low that the KE terms are also negligible.

 h1 = h 2

ie. Throttling process is a pressure drop at constant enthalpy unless otherwise mentioned.

Assuming a throttle to be a constant enthalpy process leads us to define a property called

the Joule-Thomson coefficient J as:

Positive value for  means that the fluid temperature drops during throttling process.

Negative value for  means that the fluid temperature raises during throttling process.

44
Q. Steam enters a turbine at 20 m/s & at a specific enthalpy of 3000 kJ/kg and leaves the
turbine at 40 m/s and at a specific enthalpy of 2500 kJ/kg. Heat lost to the surroundings
is 25 kJ/kg. Steam passes through the turbine with a flow rate of 3,60,000 kg/hr.
Determine the output from the turbine in MW.

Ans.

Q + m1 (h1 + C12/2 + g1z1) = W + m2 (h2 + C22/2 + g2 z2)

C1 = 20m/s, C2 = 40 m/s, Q = - 25 kJ/kg

h1 = 3000 kJ/kg, h2 = 2500 kJ/kg, m = 360000/3600 =100 kg/s, W/s =?

ie, -25 x 103 + (3000 x 103 + 202) = W + (2500 x 103 + 402/2)

W = 3000 x103 + 202/2 – 25 x103 – 2500 x 103 - 402/2 = 474.4 x 103 J/kg

Mass flow/sec = 360000/3600 = 100 kg/s

WD/sec = 474.4 x 103 x 100 kW = 47.44 MW

Q. A steam turbine receives steam at the rate of 22700 kg/hr when it is delivering 500
kW power. The inlet & outlet velocities of steam are 75m/s & 300 m/s respectively. The
inlet pipe is 3m above the exhaust pipe. Neglecting the heat lost from the turbine, find
the change in enthalpy per kg of steam.

Ans.

Q + m1 (h1 + C12/2 + g1z1) = W +m2 (h2 + C22/2 + g2 z2)

C1 = 75m/s, C2 = 300 m/s, W = 500 kJ/s

z1 = 3 m, z2 = 0 m, m = 22700/3600 = 6.31 kg/s, Q = 0, (h1 – h2) =?

[(h1- h2) + (C12 – C22)/2 + (z1- z2) g] m – W = 0

45
Therefore,

[(h1- h2) + (752 – 3002)/2+ (3 - 0) 9.8] 6.31 – 500 x 103 = 0

ie, [ (h1- h2) – (42187.5) + 29.4] 6.31= 500 x 103

h1 - h2 = (500 x 103 )/6.31+ (4.2187.5 – 29.4) = 121.397 kJ/kg

Q) A centrifugal air compressor used in gas turbine power plant receives air at 100 kPa
& 300 K. It discharges air at 400 kPa & 500 K. The velocity of the air leaving the
compressor is 100 m/s. Neglecting the velocity at the entry of the compressor, determine
the power required to drive the compressor for a mass flow rate of 5 kg/s. Neglect any
heat transfer. Take CP (air) = 1 kJ/kg K.

Ans.

Q + m1 (h1 + C12 /2 + gz1) = W + m2 (h2 + C22 /2+ gz2)

P1 = 100 kPa, P2 = 400 kPa, T1 = 300 K, T2 = 500 K, m = 5 kg/s, C1 = 0

Cp = 1 kJ/kg K, W/s =?

ie, [(h1 –h2) + (C12 – C22)/2 ] m = W

But, ∆h = Cp∆T

ie, [CP (T1 – T2) + (C12 – C22 )/2] m = W

[1 x 103 (300 - 500) + (02 1002)/2] 5 = W

(-200 x103 - 5000)5 = W

ie, W/s = -1025000 J/s

or Power = -1025 kW

Q. Air flow steadily at the rate of 0.5 kg/s through an air compressor, entering at 7m/s
velocity, 100 kPa pressure, and 0.95 m3/kg volume, and leaving at 5m/s, 700 kPa &

46
0.19m3/kg. The internal energy of the air leaving is 90 kJ/kg greater than that of air
entering. Cooling water in the compressor jackets absorbs heat from the air at the rate of
58 kJ.

a) Compute the rate of shaft work input to the air in kW.

b) Find the ratio of the inlet pipe diameter to outlet pipe diameter.

Ans.

C1 = 7 m/s, C2 = 5m/s, Q = -58 kW, P1 = 100 kPa, P2 = 700 kPa

V1 = 0.95m3/kg, V2 = 0.19m3/kg, m = 0.5 kg/s, d1/ d2 =? W =?

Q + m1 (h1 + C12 /2+ gz1) = W + m2 (h2 + C22 /2+ gz2)

ie, Q + m1(u1 + p1v1 + c12/2 + gz1) = W + m2 (h2 + c22/2 + gz2)

- 58 x 103 + 0.5[-90 + (100 x 103 x 0.95 – 700 x 103 x 0.19) + (72 – 52)/2] = W

ie, -58000 + 0.5 [-90 x 103 – 38000 + 12] = W

ie, W = -121.994 kW

From mass balance, A1C1/ V1 = A2C2 /V2

ie A1/A2 = C2/C1 x V1/ V2 = 5/7 x 0.95/0.19 = 3.57

A =  d2/4

ie d1/ d2 = 3.57 = 1.89

47