Académique Documents
Professionnel Documents
Culture Documents
E)
UNIT - 2
Basic Concept of Thermodynamics
3. It concerns itself only with the initial and final states of a system and gives no information about the
path taken (mechanism) by a process.
1
Notes Also Avail. On sachinchaturvedi.wordpress.com
2.
3.
4.
Open system: The system which can exchange matter and energy with the surrounding is called open
system, e.g., a cup of tea is an open system because it will become cold as well as its taste will also change,
i e., it is exchanging energy and matter with the surrounding.
5.
Closed system: It can exchange energy but not matter with the surroundings, e.g., tea placed in a closed
kettle.
6.
Isolated system: It can neither exchange heat nor matter with the surroundings, e.g., tea placed in thermos
flask.
7.
Homogeneous system: A system is homogeneous when it is completely uniform throughout, i.e. consists
of one phase only, e.g., a pure solid, a pure liquid, a true solution, etc.
8.
Heterogeneous system: A system is heterogeneous when it is not uniform throughout, i.e. it consists of
two or more phases, e.g., a mixture of two solids or two or more immiscible liquids, a solid in contact with
a liquid, a liquid in contact with its vapours.
9.
Macroscopic system: When system consists of large number of atoms, molecules or ions, it is called
macroscopic system.
10.
Microscopic properties: The properties associated with a macroscopic system, i.e. pressure, volume,
temperature, density, composition, viscosity, surface tension, refractive index, colour, etc.
11.
State of the system: A system is said to be in definite state when its macroscopic properties have definite
values.
Or
It is the condition of the system at an instant of time as described or measured by its properties or each
unique condition of a system is called state.
2
Notes Also Avail. On sachinchaturvedi.wordpress.com
1 2 . State variables: The macroscopic properties of a system are state variables since change in any of these
properties, causes the system to change into another state.
13.
Properties of steam
a) Extensive property of a system: It is the property which depends upon mass of the system, e.g.,
volume, pressure, internal energy, free energy, etc.
b ) Intensive property: The property which does not depend upon mass of the system, e.g.,
temperature, density, viscosity, refractive index, surface tension, specific heat, pressure etc.
14.
Thermodynamic equilibrium: if the temperature & pressure at all points are same; there should be no
velocity gradient; the chemical equilibrium is also necessary. System under temperature & pressure
equilibrium but not under chemical equilibrium are sometimes said to be in metastable state equilibrium
conditions. It is only under thermodynamic equilibrium condition that the properties of a system can be
fixed.
Thus for attaining a state of thermodynamic equilibrium the following three types of equilibrium
states must be achieved:
a) Thermal equilibrium: A system is said to be in thermal equilibrium, when there is no
temperature difference between the parts of the system or between the system and the
surrounding.
b) Mechanical equilibrium: a system is said to be in mechanical equilibrium, when there is no
unbalance force acting on any part of the system as a whole.
c) Chemical equilibrium: a system is said to be in chemical equilibrium, when there no chemical
reaction within the system and also there is no movement of any chemical constituent from one
part of the system to the other.
15.
Isothermal process: The process in which temperature of the system remains constant at each stage of the
process i.e., dT or T = 0
16.
Exothermic process: The process in which heat is given out to the surroundings is called exothermic
process. In this process, products are more stable than reactants because they have lower energy.
17.
Endothermic process: The process in which heat is absorbed by the system from the surroundings. In this
process, products are less stable than reactants because they have higher energy.
18.
Adiabatic process: The process in which no exchange of heat takes place between system and
surroundings, i.e. dq = 0 or q = 0
Note:
a. In adiabatic expansion of an ideal gas, the internal energy of the system decreases and the temperature
falls.
b. In adiabatic compression of an ideal gas, internal energy of the system increases and the temperature
rises.
3
Notes Also Avail. On sachinchaturvedi.wordpress.com
20.
Isobaric process: The process which takes place at constant pressure is called an isobaric process, e.g.,
heating of water to its boiling point and its vaporization occurs at the same atmospheric pressure.
Expansion of a gas in an open system is also an example of isobaric process in which dP or P = 0
21.
Isochoric process: The process which is carried out at constant volume is called isochoric process, i.e., dV
or V = O. e.g., E, measurement at constant volume is isochoric process.
22.
Reversible process: A reversible process is one which can be stopped at any stage and reserved so that the
system and surrounding are exactly restored to their initial states.Eg:
a) Frictionless relative motion.
b) Expansion and compression of spring.
c) Isothermal expansion or compression.
23.
Irreversible process: An irreversible process is one in which heat is transferred through o finite
elements.eg:
a) Relative motion with friction.
b) Combustion.
c) Diffusion.
d) Heat transfer.
24.
State function: The thermodynamic property which depends upon initial and final state of the system not
on the means how the state is reached are state functions.
Work
It refers to the energy transferred because of a property difference, other than temp .., that exist b/w the system &
its surrounding.
4
Notes Also Avail. On sachinchaturvedi.wordpress.com
(dv = A.dx)
1
if the piston moves through a finite distance, the W.D by the piston can be evaluated by integrating
b/w the initial & final states.
The expansion of the system (gas) by outward movement of the piston can be represented on P-V
diagram. The shaded area represents the W.D due to small movement of the piston & the total W.D by the gas
during expansion process is
When a system does +ve work, its surrounding do equal amount of ve work, the system does an equal
amount of ve work. Thus in any process
Wsystem + Wsurrounding = 0
E.g.
A gas undergoes a reversible non-flow process according to the relation P = (-3V +15) where V is the volume in
m3 & P is the pressure in bar. Determine the W.D when the volume changes from 3 to 6 m3 .
Solu :- given P = (-3V +15) bar
E.g.During a particular process, the specific heat of the working fluid comprising a system is given by the
relation
C = (0.2 + 0.002T) KJ/kg K.
Where T is the absolute temperature in degree K. what amount of heat is required to be supplied to this
fluid system to raise its temperature from 300 to 400 K? Also determine the mean value of specific heat.
Solu: the total heat interaction for change in temperature from T1 to T2 :
Q = 180KJ
The specific heat is given by
Q = mcm(t2-t1)
180 = 2cm(400-300)
cm = 0.9 KJ/kg K
Laws of thermodynamics
There are four laws of thermodynamics which are: Zeroth Law of Thermodynamics
1st law of thermodynamics
Second law of thermodynamics
Third law of thermodynamics
Zeroth Law of Thermodynamics
Two bodies are said to be in thermal equilibrium if no transfer of heat takes place when they are placed in
contact. We can now state the Zeroth law of thermodynamics as follows:
If two bodies A and B are in thermal equilibrium and A and C are also in thermal equilibrium then B and
C are also in thermal equilibrium.
It is a matter of observation and experience that is described in the Zeroth law". It should not be taken as
obvious. For example, if two persons A and B know each other and A and C know each other, it is not necessary
that Band C know each other.
Thermal Equilibrium
Body A
Thermal Equilibrium
Body B
Thermal Equilibrium
C
Body C
The Zeroth law allows us to introduce the concept of temperature to measure the hotness or coldness of a body.
All bodies in thermal equilibrium are assigned 'equal temperature. A hotter body is assigned higher temperature
7
Notes Also Avail. On sachinchaturvedi.wordpress.com
than a colder body. Thus, the temperatures of two bodies decide the direction of heat flow when the two bodies
are put in contact. Bent flows from the body at higher temperature to the body at lower temperature.
First law of thermodynamics
It states that, energy can neither be created nor be destroyed, it changes only its form.
Or
When a system undergoes a thermodynamic cycle then the net heat supplied to the system from the
surrounding is equal to net work done by the system on its surrounding.
Or
Cyclic integral of work transfer is equal to cyclic integral of heat transfer
8
Notes Also Avail. On sachinchaturvedi.wordpress.com
L i m i t a t i o n : energy can flow from from higher temperature to low temperature body but not able to flow
from lower to higher without assistance it sets no limit to the amount of total energy of a system which can be
caused to flow out as work or does not specify the condition under which conversion of heat into work is
possible.
Second law of thermodynamics
It accommodates two laws inside it which are clasius, Kelvin and Planck in slightly different words although
both statements are basically identical and based on irreversible process. The first consider transformation of heat
b/w two thermal reservoir while the second one transformation of heat into work.
Clasius statement : According to this theory it is impossible for a self acting machine working in a cyclic
process, to transfer heat from a body at a lower temperature to a body at a higher temperature body
without the aid of external agency.
9
Notes Also Avail. On sachinchaturvedi.wordpress.com
Q
Perpetual motion
machine
W=Q
Without violating the first law, a machine can be imagined which would continuously absorb heat from a
single thermal reservoir and convert this heat completely into work. The efficiency of such a machine would be
100%.this machine is called PMM2.
A practical heat engine exchanges heat with two thermal reservoirs (source & sink) & its thermal
efficiency is given by:
10
Notes Also Avail. On sachinchaturvedi.wordpress.com
This implies that at absolute zero temperature, the entropy ceases to be a function of state & approaches a
constant value independent of the parameters of the state.
This law is helpful in
Measurement of chemical affinity, i.e., the action of chemical forces of the reacting substance.
Explaining the behaviour of solids at very low temperature.
Analyzing the chemical & phase equilibrium.
Sign conventions:
1
Q is +ve when heat is absorbed,
Q is -ve if heat is evolved
2
W is +ve when work is done on the system, W is -ve when work is done by the system
Concept of Internal energy
It is sum of all the forms of energies that a system can possess. It made of 6 components:
a.
b.
c.
d.
e.
f.
Note:
a.
b.
c.
d.
e.
Enthalpy (H)
It is defined as total heat content of the system i.e. sum of internal energy and product of pressure & Volume.
The total enthalpy of mass m, of a fluid can be
H=U + PV
H is state function. The enthalpy of a fluid is the property of the fluid , since it consist of the sum of a property &
the product of the product of the two properties. Since enthalpy is a property like internal energy, pressure,
specific volume & temperature, it can be introduced into any problem wheather the process is a floe or a nonflow process.
The total enthalpy of mass, m, of a fluid can be
H = U + pV, where H = mh
Ratio of specific heats
It is the ratio of specific heat at constant pressure to the specific heat at constant volume & is represented by
(gamma).
11
Notes Also Avail. On sachinchaturvedi.wordpress.com
i.e
Since cp = cv + R, it is clear that cp must be greater than cv for any perfect gas. It follows; therefore, that
is always greater than unity. Values of for
1
2
3
Monoatomic(argon, helium)
diatomic(CO2, hydrogen, oxygen & nitrogen)
Triatomic(CO2, SO2)
= 1.6
= 1.4
= 1.3
S =
In general, the temperature of the system may change during a process is reversible, the change in entropy is
defined as
Si = initial entropy
12
Notes Also Avail. On sachinchaturvedi.wordpress.com
Entropy is a property of the system that remains constant during a reversible adiabatic process.
The reversible adiabatic process during which entropy remains constant is called isentropic process.
An interesting fact about entropy is that it is not a conserved quantity. More interesting is the fact that
entropy can be created but cannot be destroyed.
It is thermodynamic property which measures randomness or disorder of a system. The more disorder
or randomness, higher will be entropy, e.g., solid < liquid < gas. Entropy of a system is state function, i.e., it
depends upon initial and final states of the system, When the state of a system changes, the entropy also changes.
S =
The entropy of a system increases with absorption of heat & decreases with heat rejection. Its unit is KJ/K
while specific entropy is KJ/KgK.
Thermodynamic Properties of Steam
There are six basic thermodynamic properties are required
1. P (pressure)
4. U (internal energy)
2. T (temperature)
5. H (enthalpy)
3. V (volume)
6. S(entropy)
These properties must be known at different pressure for analyzing the thermodynamic cycles used for work
producing devices.
The values of these properties are determined theoretically or experimentally and are tabulated in the form of
tables which are known as 'Steam Tables'.
Following are the thermodynamic properties of steam which are tabulated in the form of table:
p = Absolute pressure (bar or KPa)
ts = Saturation temperature (0C)
hf = Enthalpy of saturated liquid (kJ/kg)
hfg = Enthalpy or latent heat of vaporization (kJ/kg)
hg = Enthalpy of saturated vapour (steam) (kJ/kg)
Sf = Entropy of saturated liquid (kJ/kg K)
Also,
hfg = hg - hf
Sfg = Sg - Sf
Vfg = Vg - Vf
Tempe
rat-ure
(t) in oc
Specific volume
in m3/kg
Water
Steam
(vf)
(vg)
Evaporation
(hfg)
Steam
(hg)
6.983
13.04
60.09
0.001000
0.001001
0.001017
129.21
87.982
7.649
29.3
54.7
251.5
2514.4
2525.5
2609.9
0.106
0.196
0.832
(sfg)
8.871
8.634
7.077
8.977
8.830
7.909
0
5
10
Absolu
te
pressur
e (p) in
bar
0.00611
0.00872
0.01227
Specific volume
in m3/kg
Water
Steam
(vf)
(vg)
Evaporation
(hfg)
Steam
(hg)
0.001000
0.001000
0.001000
0.0
21.0
42.0
2501.6
2489.7
2477.9
2501.6
2489.7
2477.9
206.31
147.16
106.43
Formation of Steam
at OC with volume Vf m under the piston. Further let the piston is loaded with load W to ensure heating at
constant pressure. Now if the heat is imparted to water, a rise in temperature will be noticed and this rise will
continue till boiling point is reached. The temperature at which water starts boiling depends upon the pressure
and as such for each pressure (under which water is heated) there is a different boiling point. This boiling
temperature is known as the temperature of formation of steam or saturation temperature. During heating up
to boiling point that there will be slight increase in volume of water due to which piston moves up and hence
work is obtained but this work is so small that it is neglected.
Now, if supply of heat to water is continued it will be noticed that rise of temperature after the boiling point is
reached nil but piston starts moving upwards which indicates that there is increase is volume which is only
possible if steam formation occurs. The heat being supplied does not show any rise of temperature but changes
water into vapour state (steam) & is known as latent heat. So long as the steam is in contact with water, it is
called wet steam (fig iii) & if heating is further progressed (fig iv) such that all the water particles associated
with steam are evaporated , the steam so obtained is called dry & saturated steam.
If vg m3 is the volume of 1kg of dry and saturated steam then work done on the piston will be
WD = P(vg-vf)
Where p is the constant pressure (due to piston weight W)
14
Notes Also Avail. On sachinchaturvedi.wordpress.com
hsup =hf+hfg+cps(tsup-ts)
Graphical Representation of Formation of Steam
15
Notes Also Avail. On sachinchaturvedi.wordpress.com
It is the quantity of heat required to convert 1 kg of water at saturation temp for a given pressure into dry &
saturated steam at that temperature & pressure. The value of latent heat is not constant, it decreases as the
pressure increases & becomes zero when the critical pressure is reached.
Depending upon the condition of steam, the enthalpy or heat values are defined as :
(i) Total heat of wet steam : It represents the quantity of heat required to covert 1 kg of water at 0oC into
wet steam at constant pressure
hwet = hf + x hfg
where x is the dryness fraction of wet steam
The sensible heat increases with pressure.
(ii) Total heat of dry saturated steam : It represents the quantity of heat required to covert 1 kg of water at
0oC into dry saturated steam at constant pressure
hs = hf + hfg = hg
The enthalpy of dry saturated steam increases with pressure.
(iii) Total heat of superheated steam : It represents the quantity of heat required to covert 1 kg of water at
0oC into superheated steam at constant pressure
where,
5 . S a t u r a t e d S t e a m : When the molecules escaping from the liquid becomes equal to the molecules
returning to it.
6 . S a t u r a t e d L i q u i d : The liquid at its boiling point at a specified pressure is called a saturated liquid.
7 . S a t u r a t e d V a p o u r : Saturated steam may be dry or wet, when the saturated vapour contains particles of
liquid evenly distributed over the entire mass of vapour, it is called wet saturated steam.
8.superheated steam:-when steam is heated after it has become dry & saturated , it is called superheat steam &
the process of heating is called superheating. It is carried out at constant pressure. & the additional heat supplied
during this is heat of superheat. It can be calculated as
hsup =hf+hfg+cps(tsup-ts)
16
Notes Also Avail. On sachinchaturvedi.wordpress.com
Throttling Calorimeter
The dryness fraction of wet steam can be determined by using a throttling calorimeter.
Working: The steam to be sampled is taken from the pipe by means of suitable positioned and dimensioned
sampling tube. It passes into an insulated container and is throttled through an orifice to atmospheric pressure.
Here the temperature is taken & the steam ideally should have about 5.5K of superheat.
Throttling calorimeter
Throttling process
Throttling process is shown on enthalpy & entropy i.e. h-s diagram by the line 1-2. If steam initially wet is
throttled through a sufficiently large pressure drop, then the steam at state 2 will become superheated. State 2 can
then be defined by the measured pressure and temperature. The enthalpy, h2 can then be found and hence
h2 = h1 = (hf1 + Xl hfg1) at P1
[Where h2 = hf2 + hfg2 + cps (Tsup2 Ts2)]
X1 =
(h2 - hf1)
hfg1
Calculate the dryness fraction of the steam in the main. Take cps = 2.1kJ/kg K.
Solu : Condition of steam before throttling :
P1 = 8 bar, x1 =?
Condition of steam after throttling:
P2 = 1 bar, t2 = tsup = 115 oC
As throttling is a constant enthalpy process
h1 = h2
i.e.,
18
Notes Also Avail. On sachinchaturvedi.wordpress.com