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Chapter 1.

Basic concepts
1.1.Thermodynamics as a science
Thermodynamics is a science based on phenomena which studies the matter from the point of
thermal motion; it studies the body properties and energy transfer among bodies,which are
produced by internal molecular motion. The matter is made of microscopic particle which
interacts and are in perpetual motion, known as thermal motion.Thermodynamics studies the
phenomena produced at microscopic level to groups of particles investigating their
macroscopic, measurable effects and establishes relations between measures which are
observable and measurable,such as volume,pressure,temperature,concentration of chemical
solutions.
Thermodynamics stands on two relations from kinetic molecular theory:

Bernoulli relation determines the pressure of aas on a wall, a macroscopic measure, as a


function microscopic measures :
p

2 N mv 2
3V 2

N no. of molecules in volume V


m mass of a molecule
mv 2
- mean kinetic energy of molecules in translation motion,
2

Maxwell Boltzmann relation determines the connection between the temperature of a


gas and mean speed of molecules.

3
mv 2
kT
2
2
23
In which k is Boltzmann constant k 1,38 .10 J / k

In other words pressure and temperatureare measures which features the group, the assembly of
molecules, not a given molecule.
The technical thermodynamicsstudies the processes of producing, transmitting and use of
energy in its form as heat and work, applying its own laws to heat engines and installations.
Thermodynamics operates with measures and concepts which define thermal
phenomenon.Examples of thermalphenomena are as follows:
Heat transfer between two bodies having different temperatures;
Phase changes of substances ;
Transformation of heat in work and reverse in heatengines.
Main notions are thermodynamic system, state, process.

1.2 Thermodynamic systems


Generally a physical system is an area of universe made of substance or fields.

The thermodynamic system is made of a body or an assembly of bodies having a finite number
of particles,which is limited fromsurroundings through a boundary surface and which interacts
energetically.The system changes substance (mass) or energy as heat or work with the
surroundings.
An insulated system is not influenced in any way by the surroundings. This means that no heat
or work or mass crosses the boundary of the system.
An adiabatic or thermal insulated system does not change heat with the surroundings. A
mechanical insulated system does not change work with the surroundings.
Some thermodynamic analysis involves a flow of mass into or out of a device. So, we can
discuss about open systems. If there is no mass flow, the system is closed. The terms closed
system and open system are used as the equivalent of the terms system (fixed mass) and control
volume (involving a flow of mass).
The surface of a control volume is referred to as a control surface. Mass, as well as heat and
work, can flow across the control surface.
Thus, a system is defined when dealing with a fixed quantity of mass and a control volume is
specified when an analysis is to be made that involves a flow of mass.
1.3.State. State parameters
The state may be identified or described by certain observable, macroscopic properties, like
temperature, pressure, density. Each of the properties of a substance in a given state has only
one definite value and these properties always have the same values for a given state, regardless
of how the substance arrived at that state.
A state property can be defined as any quantity that depends on the state of the system and is
independent of the path (prior history) by which the system arrived at the given state.
Conversely, the state is specified or described by its properties.
Thermodynamic properties can be divided into two general classes: intensive and extensive
properties. An intensive property is independent of mass; the value of an extensive property
varies directly with the mass. Pressure, temperature and density are examples of intensive
properties. Mass and volume are examples of extensive properties. Extensive properties per unit
mass, such as specific volume, become intensive properties.
We will refer not only to the properties of a substance, but also to the properties of a system.
Then we necessarily imply that the value of the property has significance for the entire system
and this implies what is called equilibrium. For example, if a gas is in thermal equilibrium, the
temperature will be the same throughout the entire system and we may speak of the temperature
as a property of the system. We may also consider mechanical equilibrium and this is related to
the pressure. A system is in mechanical equilibrium if there is no tendency for the pressure at
any point to change with time as long as the system is isolated from the surroundings. If the
chemical composition of a system does not change with time, that system is in chemical
equilibrium. It means, no chemical reactions occur.
When a system is in equilibrium as regards all possible changes of state, we may say that the
system is in thermodynamic equilibrium.

For fluids there are at least three macroscopic measures which are state parameters,usually
pressure, temperature and volume, called fundamental state parameters. The values of
parameters of state do not depend on previous history or path of the system, depend only on
instantaneous coordinates of the system.When a system passes from a state of thermodynamic
equilibrium to another one,the variation of a parameter of state will cause the variation of other
ones,showing a dependency between parameters of state, called state equation.

1.3.1.Specific volume
The specific volume of a substance is defined a s the ratio between volume V and mass m
being noted with v (m3/kg).
v

V
m

m3

kg

The specific volume is inverse of density or specific mass kg / m 3 .


v

1 m3

kg

Volume of a kilomole of substance is called molar volume VM


VM

m3
V
V

Mv
m
n
kmol
M

The molar volume is the volume reported to number of kilomol of substances contained (nnumber of kilomol, M-molar mass).
The kilomol has two definitions :
- molar mass of a substance expressed in kilograms ( ex. 1 kmol de O2 = 32 kg as MO2 =
32kg/kmol) or
-a quantity of matter which contains inthe same conditions a number of molecules equal to
Avogadro number( 1 kmol = NA molecule = 6,023.1026 molecule).
1.3.2.Temperature
Although temperature is a property familiar to us , an exact definition of it is difficult.
From our experience we know that when a hot body and a cold body are brought into contact,
the hot body becomes cooler and the cold body becomes warmer. If these bodies remain in
contact for some time, they appear to have the same hotness or coldness.
Because of the difficulty in defining temperature, we define equality of temperature.
Consider two blocks of copper, one hot and the other cold, each one in contact with a mercury
in glass thermometer. If these two blocks are brought into thermal contact , the mercury
column of the thermometer in the hot block drops at first and in the cold block rises, but after a

period of time no further changes in height are observed. It is said that both bodies have the
same temperature when they reached the thermal equilibrium.
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. It is based on the
transitivity of the thermal equilibrium. Two systems found in thermal equilibrium with a third
one are in thermal equilibrium between them (meaning that they have the same
temperature).Based on this property, a thermometer (or more general a thermometric body = a
body having a thermometric property) can compare different thermal equilibrium states of the
bodies.
Temperature represents a parameter of statewhich describes the heating state of a system, state
dependable on the molecular energy of every component.
Temperature is a physical fundamental measure and it can be determined measuring the
variation of a physical measure,generally called thermometrical measure, which is sensitive,
preferable as linear as possible, to temperature variation. For example when we measure the
temperature of our body with a mercury thermometer we measure in fact the expasion of the
mercury produced at the contact with the body,expansion quantified by the variation of height
of mercury column in the thermometer.Otherthermometric measures are variation of the length
of a metal rod, variation of the electric resistivity (thermometer is called thermo-resistance),
variation of the thermo-electromotor voltage (thermometer is called thermocouple), variation of
a gas in a constant volume enclosure ( gas thermometer), variation of light intensity of an
incandescence source (optic pyrometers).

Bimetal strip thermometer

Glass thermometer

Thermocouple

Thermoresistance

Gas thermometer

Pyrometer

For every type of thermometer it must be set a temperature measurement scale in such a
way that temperature measurement to be done through a simple reading. Fixing the temperature
scale is called calibration and it can be done bringing thermometer in thermal contact with a
body in a reproducible state ( ex. water in thermal equilibrium with vapours , water in thermal
equilibrium with ice, melting point of some metals). To those perfect reproducible states are
associated accurate values of temperature.

S2.
1.3.2.Temperature (continued)

Thermometers have a macroscopic property that changes considerably with


temperature (for ex., the pressure of a gas, the electric resistance, expansion
etc).
If a thermometer is brought in thermal contact with a hot body (H), at
equilibrium, the variable property (for ex. the length L) changes with LH
If the same thermometer is brought through thermal contact at the
equilibrium state of a cold body (C), the same property will change with LC
The difference between LH and LC corresponds to the change in the property
of the thermometer brought in thermal contact with the two bodies. This
change characterises the difference between the temperatures of the hot body
and the cold body.
To estimate this difference, it is necessary to adopt a scale for temperature
measurements.
Based on the assumption that the temperature t and the property of the
thermometer ( for example the heigth of the mercury termometer, L) are
related linearly, it results:
dt=adLor t=aL+B.
If the thermometerisbrought in contact with a cold body, at tC
tC =aLC +B
and if the thermometerisbrought in contact with a hot body, at tH

tH=aLH+B.
For anyintermediatetemperaturebetweentC and tH ,called t, corresponds a
length L. Substituting a and B itisobtained for anyintermediatetemperature t
.
t=tC+ OB
OB/CE=OA/AE -Thales theorem
OB=(OAxCE)/AE=(L-Lc)(tH -tC) /(LH-LC)
t =tC+ (L-Lc)(tH -tC) /(LH-LC), based on interpolation formula and similarity
of triangles.

This is the equation of any empirical temperature scale.An empirical


temperature scale is a scale based on the properties of a given substance. In
order to compare the measurements of different thermal states, these must be
submitted to the same thermal states. For example for empirical scale
Celsius there were adopted two fixed, easily reproducible points, based on
water properties, the ice point point and the steam point.
The temperature of the ice point is defined as the temperature of a mixture of
ice and water, which is in equilibrium with saturated air at a pressure of 1
atm.
The temperature of the steam point is the temperature of water and steam,
which are in equilibrium at a pressure of 1 atm.

A line of equal ratios can be written which define different temperature


scales Celsius, Reaumur, Fahrenheit, Kelvin, Rankine:
(L-LC)/(LH-LC) = (t-tC)/(tH-tC) = tC/100 = tRe/80 = (tF-32)/180 = (TK273.15)/100 = (TR-491.67)/180
or
tC = 5tRe/4 = 5(tF-32)/9 = TK-273.15 = 5(TR-491.67)/9
K

212 0F

373,15K

100 C

273,15K

0C

0K

-273,15 C

32 F
0

-460 F

On Celsius scale00C coresponds to a mixture water and ice at


equilibrium and 1000C to boiling water. A Celsius grade equals a Kelvin
grade, onlyorigins of scales are different.
There are several temperature scales different through the origin of the scale
or the magnitude of the unit (grade or degree). Celsius scale considers zero
value to the temperature at which water solidifies and 100 value to the water
vaporisation temperature, at normal atmospheric pressure Fahrenheit scale
considers 32 and respectively, 212F to the same water temperatures (Some
historical sources said that zero Fahrenheit is the temperature of brine
solidification ( -17.8 C) and 100 F (37.7 C) is the max. temperature of
human body). These two scales are defined based on well known and
reproducible temperatures.
In thermodynamics it was considered to find a temperature scale
independent of the properties of a particular substance. Such a scale is called
a thermodynamic scale or an absolute temperature scale. This scale was
imagined starting from the properties of ideal gas when there is a variation
of its pressure with temperature.If it was considered a gas thermometer
having a constant volume it was noticed that in the field of low pressures the
gas temperature is proportional with gas pressure (at constant volume)Or it
can be written that gas temperature T varies linearly with gas pressure p or
T = a + bp,
in which a, b are constants of the gas thermometer. Such a scale is called
temperature scale of ideal gas and can be determined measuring gas pressure

at two reproducible temperatures such as water solidification and


vaporization at normal atmospheric pressure and the equation is determined
knowing a and b for Celsius scale. If the nature of the gas is changed from
A to B then similarly can be determined two points and another proportional
line like in fig.1.

Gas A

Gas B

-273,15

t (C )

Figure 1. Relation between pressure and temperature for gas thermometer


It can be noticed that no matter the nature of the gas the two lines intersects
in a point corresponding to zero pressure and correspondent temperature to
this point is -273.15C.This temperature is the lowest reachable temperature
attributing zero value and the scale is called Kelvin scale. At this
temperature the gas molecules are no longer in motion The value of a
constant is zero and equation T = bp, meaning that it is enough one point to
define an absolute temperature scale. It is considered that the absolute
temperature scale is identical with thermodynamic scale in the field of linear
variation of ideal gas, thus meaning all temperature range excepting very
low temperatures to which condensation appears and very high temperatures
to which dissociation and ionisation appear.
Relation between Kelvin scale and Celsius scale is
tC = TK273.15 .
A degree Celsius isequal to a Kelvindegree,1C=1 K,but the
origins of the scales are different.Fahrenheit scalediffersfromKelvinscale
and Celsius scalethrough the origin of the scale and magnitude of the
unit.Theconnectionbetween Fahrenheit and Celsius scalesisgiven by relation
:
tF = 1.8tC + 32 .
In
the
British
units
system
thereis
an

absolutetemperaturescalecalled Rankine in whichabsolutezeroisidentic to


absolutezero in Kelvin scale , but the magnitude of the degreeisdifferent
1R=1,8 K.
Relation of transformation between Rankine and Celsius degreesis
tR = tF + 459.67
A degree Rankine equals a degreeFahrenheit,1R=1F,but the
origins are different.
In thermodynamiccalculationsitisusedabsolutetemperatureexpressed in
Kelvin.

Chapter 1.Basic concepts


1.3.3 Pressure
Pressure is defined as normal force applied on unit of surface, for a static
fluid,pressure gas the same value on any direction. For fluids it used
hydrostatic pressure expressed as p g h ( - density of the fluid, ggravitational acceleration, h - the height of the fluid column).
Pressure is classified according to the method of measurement in:
- Absolute pressure (p) pressure measured reported to absolute
vacuum
- Relative pressure (pr) pressure measured reported to atmospheric
pressure (pa)
pr p pa

The technical gauges measure relative pressure pr.


Manometers measure the increase of pressure from atmospheric pressure,
the pressure calledmanometric pressure (pmanom) or supra pressure,when
p p a ,and p man p p a
Vacuum-metersmeasure the decrease of pressure from atmospheric pressure,
pressure called vacuum-metric pressure or vacuum pressure pvor(pvac) when
p p a ,and
p vac p a p

When p p a in calculation is usedalso another indicator called vacuum


expressed in percentage:
vacuum %

pr
p
100% vac 100%
pa
pa

In other words the absolute pressure is measured reported ( or having as


reference ) the absolute vacuum :

p=pa pr
in which it is considered the plus sign when relative pressure is an over
pressure called manometric pressure pr=pmand the minus sign when relative
pressure is a loss of pressure called vacuum pressure pr=pv.
Barometers measure absolute atmospheric pressure pbar.
In thermodynamic calculation, it is used the absolute pressure.

Relations between pressure units


N/m2

Unit

kgf/m2

bar

10-5

at
kgf/cm2

atm

0.102.10-

0.987.10-

torr
mm Hg

mm H2O

750.10-5

0.102

0.987

750

0.10.105

10-4

9.68.10-5

735.6.10-4

104

0.968

735.6

104

1.013

10.332

1.013

760

1.013.104

1.333.10-

13.6

13.6.10-4

1.32.10-3

13.6

10-4

9.68.10-5

735.6.10-4

1
N/m2=Pascal

0.102

1 bar

105

0.102.105

1.02

1 kgf/m2

9.81

9.81.10-5

1 at
1kgf/cm2

9.81.104

0.981

1 atm

1.013.105

1 torr
1mm Hg

133.3

1mmH2O

9.81

9.81.10-5

-A physical atmosphere 1 atm = 101325 N/m2 = 10.332.276 kgf/m2 = 760 torr.


-1bar = 105N/m2
-A technical atmosphere 1at =1kgf/cm2=9.81.104N/m2 .
-Equivalent pressure of 1mm column of mercury is called torr
1 torr = 133.3223 N/m2 = 13.5951 kgf/m2 = 13.15789.10-4 atm.
-Equivalent pressure of 1mm column of water
1 mm H2O=9.81N/m2

In order to compare the properties of gaseous substances they must be in the


same state of pressure and temperature. It was defined a standardized state
called normal physical state by:
p N 760 mmHg 1.033 kgf / cm 2 1.013 bar

TN 273 .15 K or t N 00 C

In thermodynamics is used a unit of volume measurement-normal cubic


meter 1 m N3 which is a unit of volume but also a unit of mass, representing
the mass of gas contained in a volume of 1 m3in the conditions of normal
physical state ( at pNand TN).
There is also a tolerated unit called normal technical state defined by:
pn 1kgf / cm 2 0.981 bar
Tn 293 .15 K tn 20 0 C

1.3.4. Density (specific mass)


Density is the mass of unit of volume,being the reverse of specific volume.

m kg

V m3

In thermodynamics it is used also specific gravity defined as

mg N

V m3

or g .
1.4.Process measures. Work and heat
The thermodynamic process or state transformation is a physical
phenomenon in which the bodies exchange energy in form of heat and
mechanic work.As a consequence of energy variation the thermodynamic
system modifies its state of energetic balance meaning the modification of
thermodynamic state. A thermodynamic transformation means the passing of
a thermodynamic system from an initial equilibrium state to a final
equilibrium state,through continuous,successive, intermediate equilibrium
states. Any thermodynamic process is featured by specific measures called
process measures which depend on the path the system passes that mean
they depend on intermediate states of the system.The intermediate state can
be equilibrium states or not. Classification of thermodynamic processes can
be done after several criteria.
a. After relative variation of state parameters:

Differential processes or infinitesimal for which the relative


variation of state parametersis very small;

Finite processes when at least one parameter suffer a relatively high


variation.

b. After the nature of intermediate states:

Quasistatic processes (at equilibrium ), in which intermediate states


can be considered close enough to equilibrium states in every moment
of the process;
Nonstatic processes, in which intermediate states of the system
cannot be completely described from a thermodynamic point of view.

When a thermodynamic system leaves the equilibrium state, after a period of


time called time of relaxation, it recovers its initial state. When the
thermodynamic processes performs with smaller speeds than relaxation
speed, in any step of the process, the state parameters have values
corresponding to equilibrium state and it is said that the process is
quasistatic. Real processes are non static and quasistatic processes are only
approximations of real processes.Quasistatic processes can be represented in
diagrams, for example in p-V ( pressure volume), by means of a continuous
line between initial and final state,(fig.2a) andnon-static processes cannot be
represented like a continuous line because in the intemediate states which
are not in equilibrium the state parameters have not a unique value for the
whole system (fig.2b).

i
f

(a)

(b)

Fig.2 Representation of quasistatic (a) and non-static processes (b).


c. After the procedure of passing from the initial state (i)into final state (f)
and reverse, the thermodynamic processes can be divided in:

Reversibile process, in which the system passes from initial to final


state directly and reversely,exactly through the same points, on the
same path.

In order to perform such a process, the external conditions should modify


extremely slow so the system to adapt progresively to the new variations
which gradually appears;

Non reversible process, in which the system passes from initial to


final stateand reversed through different points,on other path.

Real processes cannot be considered reversible .A process can be considered


reversible if intermediate states when passing from initial to final state are
close enough to intemediate states when passing from final to initial state.
d. After connection between initial and final state:

Cyclic processes when initial state is the same with final state;

Non cyclic processes (open), when initial state differs from final
state.
Work and heat are macroscopic formsof energy transfer between bodies
Work and heat do not feature the state of the system at a given moment (they
are not state parameters).Work and heat represent specific process measures.
Work and heat are not forms of energy, but forms of energy transfer.
1.4.1.Work
Let us consider a gas in a cylinder of an internal combustion engine which
expands and actuates upon the piston. Hitting the piston wall the molecules
modify axial components of the speeds; the variation of molecular energy
will transmit to piston as work,which is a ordered form of energy transfer
because it affects only one direction components of the molecular speeds.
Work sums at macroscopic level (piston motion) the effect of molecule
motions.
In mathematical calculations there are used three formulas for work. In
English literature the abbreviation of work is W,in Romanian one is L
(Lucrumechanic-Mechanic Work).
a) Work produced by state transformation (Boundary work)
It is considered an enclosure with gas at pressure p.Outside the enclosure
there is external pressure pe. In time interval dthe volume of gas is
increasing with dV. For an elementary surface dSfrom initial surface with

the versor of normal direction and dn the motion of dSon normal


direction.Integrating on the whole volume V it results the relation for
elementarywork L by variation of the volume as result of pressure forces.
L pe dSdn
v

L p e dV

Last formula expresses the mechanical work produced modifying the


volume of the fluid as a consequence of pressure forces.
Observations
1) Because workis not a state parameter,its elementary variation id not a
total differential -so Lrepresent a infinitesimal quantity of work .
Finite work released or consumed in a thermodynamic process when
passing from an initial state 1 ( parameters p1,V1, T1) to a final state 2 (
parameters p2,V2,T2) is noted with:
2

L1 2 L , never L2 L1 L

2) In relation of work appears pe and L p e dV


If external pressure is identical with internal pressure p e p or pe p dp ,
then L pdV (neglecting the infinitesimals of second order ).
These conditions are met when the processes are reversible and quasi-static.
In thermodynamic calculations all real processes are replaced with
equivalent quasi-static processes and elementary work is calculated with
formula L pdV ,in which p pressure of the fluid .
The signs of the work are deducted for the elementary work formula.
L pdV

As p 0 then the sign of work is given by the sign of variation of elementary


volume:in expansion processes dV 0 L 0 L12 0 , the performed work
towards exterior of the system is positive; similar, in compression processes,
dV 0 L0 L12 0 ,and the work received by the system ( performed by
exterior upon the system) is negative.
Graphical representation of the processes - It is considered the expansion
process
from
figure,
from
initial
statei
to
final
state

f.
p
i
pi

f
pe
V
Vi

Vf

Fig.3 Work of the state transformation


The work of the expansion process ispdV, in which :
L pdV

and L is elementary work given by a current value of the pressure (pressure


is considered constant for a infinitesimal variation of volume dV)
2

L1 2 pdV
1

The work is equal to area under curve made with abscissa V.From graphic it
is noticed that transformation i-f or 1-2 can actuate also on other paths and
work of the transformation 1-2 could have different values according to
specific path (intermediate states ) on which the system works. In other
words in the transformation from state 1 to state 2, the work depends on the
path of the transformation.
b)Flow Work (work consumed to actuate a fluid)
Considering a pipe through which a fluid is flowing,if we imagine three
zones of the same lengthl at constant pressure p = constant.It is called work
consumed to actuate a volume of fluid V in an environment of constant
pressure p or flow work ,the product
Ld pSl pV

Ld work consumed to actuate a volume of fluid V at constant pressure p.


The fluid from area I actuates upon the fluid from area II,the fluid from
area II actuates upon the fluid from area III and so on resulting the motion of
the fluid. This type of work does not increase fluid energy, Ldcontributes

only tothe increase of energy of the fluid accumulated in the reservoir at the
end of the flow pipe.
One of the forms of energy applied to a fluid is enthalpy, I, being the sum
between U, internal energyand product pV.
enthalpy I U pV J .
c)Shaft work is the total mechanical work performed upon or consumed by a
heat engine taking into account both the thermodynamic processes of the
working agent in the engine and intake and exhaust processes into and
outside engine. It is considered the same source of working agent which
enters and leave the engine.
2

Lt pdV Ladm Lev


1

Ladm L'd flow.work p1V1 received


Lev L"d flow.work p2V2 released
2

Lt pdV p2V2 p1V1 pdV d pV Vdp


2

Lt Vdp - shaft work is the total work produced or consumed by a


1

working agent in a heat engine.The shaft work is equivalent to area between


the graphic of state transformation and coordinate axis of pressure p.
p
i
pi

f
pe

V
Vi

Fig.3. Shaft work of a state transformation

Vf

1.4.2.Heat exchange
Heat is classified in sensible heat and latent heat. Sensible heat is related to changes
in temperature of a gas or object with no change in phase (I).Latent heat is related to
changes in phase between liquids, gases, and solids (II).
Heat is a form of macroscopic transfer of energy, generally produced between two
bodies with different temperatureswithout mechanical interactions.
What is called exchange of energy as heat at macroscopic scale is an exchange of
molecular kinetic energy at microscopic level.
When water is heated in a bowl by a flame, the amplitude of the molecule motion is
increased.The molecules of the fluid took the energy from the bowl, the water
temperature increases (sensible heat) and there is an exchange of kinetic energy from
gas to water. Heat is a disordered form of energy transfer the flame contains highly
activated molecules.
The heat exchange inan elementary process is expressed
Q mcdt

in which m mass of the body , c- real specific heat and dt- difference of
temperature.
2

t2

t2

t1

t1

For a chemical process Q12 Q mcdt m cdt


As heat is not a parameter of state (it is not a form of energy,but a form of transfer of
energy), Q is not a total exact differential.
Heat is considered positive when the system receives energy from environment and
negative when the system releases energy to the environment.
1.5.Specific heats
(I).It was experimentally noticed that in order to heat (or cool) different bodies with
the same number of degrees are required different heat quantities. So in order to
describe substance from this point of view it was introduced the term caloric
capacity.The caloric capacity is the ratio between the heat Q in an elementary
process and the corresponding variation of its temperature dT,
dQ
C
.
dT

Caloric capacity can be also defined as the physical quantity of heat absorbed by a
body in order to modify its temperature with 1 unit (1 grade). Unit of measure is J/K.
Specific heat is a physical property of the substances which depends on the
nature,phase of the body, temperature and for gases,on the nature of thermodynamic
process in which the heat transfer is done ( at constant pressure or at constant
volume). Specific heat or the caloric capacity of unit of mass is the physical measure
numerically equal to sensible heat quantity exchanged by unit of mass of a body with
the surroundings in order to modify its temperature with 1 unit. Between specific heat
c and caloric capacity C, there is the following relation: C = mc

Specific heat can be classified according to unit of substance reported as follows:


a) Specific heat reported to 1 kg of mass (mass specific heat)

Q J
c
mt kgK

Q mcdt

with m, the mass of the body expressed in kg, t is temperature variation of the
body, in degrees .
b) Specific heat reported to 1 kmol of substance (molar specific heat )

Q J

cM
k molK
n

Q nc dt
M

with n, number of kilomoles , t is temperature variation of the body,in degrees.


c) Specific heatreported to 1 m N3

Q J
C N

VN t mN3 K

Q VN C N dt

with VN, volume expressed in normal state, t is temperature variation of the body .
A gas can be heated ( or cooled) in several ways, keeping some parameters constant.
A gas can be heated at constant volume or at constant pressure. Experiments showed
that the heat at constant pressure of the same amount of gas for the same difference of
temperature is higher than the heat at constant volume (of the same amount of gas
for the same difference of temperature). In other words a gas can have two specific
heats according to the nature of the process:
- Specific heat at constant pressure (marked with index p)
J
J
J
cp
; cM p kmolK ; C Np m 3 K
kgK

- Specific heat at constant volume (marked with index v)


J
J
J
cV
; cMV
; C NV 3

kmolK
kgK
mN K

For gases , cp and cv have different values (cp>cv) but to solid and liquid substances
the difference between values is very small and is neglected.
There are the following equivalent relations between the three types of specific heats
cM Mc 1kmol M kg

3
cM 22.414 C N l kmol 22.414 mN Avogadro

The expressions above can be explained like this:


Molar specific heat is equal to the product between molar mass of the gas (M) and
mass specific heat (c).
Molar specific heat is equal to the product between the constant 22.414 and specific
heatreported to 1 m N3 (CN).

Specific heat of bodies increases with the increase of temperature the variation c=c(t)
can be done graphically or analytically.
Analytically c is made of a sum of polynomials which follow the form of graphic:
c a bt dt 2 et 2 ft 3 gt 3 .......

or. for .linear


c a b t
1
1

The specific heat values depend on the nature of substances and vary with
temperature;their values are measured and can be found in thermodynamic tables.
( http://www.engineeringtoolbox.com/specific-heat-solids-d_154.html,http://www.engineeringtoolbox.com/specificheat-fluids-d_151.html,http://www.engineeringtoolbox.com/spesific-heat-capacity-gases-d_159.html)
Example Air properties
Temperature
(oC)

Density
(kg/m3)

Specific heat cp (kJ/kg.K)

-100

1.980

1.009

1.293

1.005

40

1.127

1.005

80

1.000

1.009

140

0.854

1.013

180

0.779

1.022

250

0.675

1.034

300

0.616

1.047

400

0.524

1.068

a) In order to select c values according to temperature variation it is considered the


linear variation of c p , cV , cM , cM , C p , CV
b) It can be considered also average (mean) values of c given between t0 and t.
p

c p m c p tt 0 f t

Considering the hypothesis of linear variation

cm c tt0 ct tm

or cm

t1 t2
2

t 2 c tt02 t1c tt10


t 2 t1

In thermodynamic applications, to make the calculations easier specific heats are


approximated to average values between two temperatures.
II.Latent heats
The word latent comes from Latin latere, meaning to lie hidden. There are thermal
processes in which even the heat is transmitted to the body, its temperature does not
vary (ex. melting or vaporization)so the heat exchange is not sensitive, is latent
(hidden) and it cannot be measured with a thermometer. In this case the heat
transmitted is used for the change of phase of the body and in this situation a new
caloric coefficient is defined, called latent heat for phase transformation ( latent heat
of vaporization, latent heat of fusion)
Q

,
m

This coefficient is defined as heat quantity required for changing the phase of the unit
of mass from a substance,at a constant temperature and pressure. The unit is
J/kg,being an intensive measure. For the same substance the latent heat of
vaporization is equal to latent heat of condensation and the latent heat of fusion is
equal to latent heat of solidification.

Questions
1. What studies thermodynamics ? Give examples of thermal phenomena.
2. What is a physic system?What is a thermodynamic system ?
3. What is an isolated system?
4. What is the difference between an open and a closed system ?
5. How do you express the state of a system ?
6. What is thermodynamic equilibrium ?
7. What are extensive parameters ? What are intensive parameters ?
8. How is classified pressure according to measurement method ?
9. What type of pressure is measured with manometers and vacuum-meters ?
10.What type of pressure is measured with barometer ?
11.What property is described by temperature?
12.What is a thermal measure (or quantity) ? Do you have some examples ?
13.Can be directly measured the temperature of a body ? Why ?
14.How do you enounce the zeroth law of thermodynamics?
15.What is a scale of temperature ?
16.How do you classify the scales of temperature and which are they?
17.Which are the relations between the origins and units of the scales ?
18.How was determined the lowest temperature and what is its meaning ?
19.How is defined the specific volume?
20.How is defined the molar volume ?How is defined the kilomole?
21.Which are normal physical gas state ?
22.How is defined the density ? How is defined the specific gravity ?
23.What are finite thermodynamic processes ?
24.What is the difference between quasi-static and non-static processes?
25.When a process is reversible ?When a process is irreversible ?
26.What is mechanic work ?

27.How is classified work in thermodynamics ?


28.In p-V representation of a transformation of state of a gas which is the
significance of the boundary work ( work of the state transformation ) But of
the shaft work ?
29.Which is the sign rule for work?
30.What is heat ?Is a quantity of state or a process?
31.Which is the sign rule for heat ?
32.How is expressed the heat change which produces the heating of a body ?
33.How is expressed the heat change which produces the change of phase of a
body ?
34.What is specific heat ? How is reported to different units of mass ?
35.Is specific heat constant with temperature ?

Chapter . 2. First law of thermodynamics


Some calculations and experiments performed in the XIX th century demostrated that
mechanical work and any other form of energy can be transformed in heat and
reversed and it was determined the equivalency ratio of transformation.In technical
system heat is expressed in kilocalories ( a calorieis the amount of heat (energy)
required to raise the temperature of one gram of water by 1 C)and work in
kgf.m(work produced moving a body of 1 kg on a length of 1 m),those units being in
that period considered as independent.
In 1842 Robert Mayer introduces the mechanical equivalent of heat unit and
determined its value by calculations, in the same year Joule determined the caloric
equivalent of work and Helmholtz demostratedthe equivalence between the thermal
and mechanical energy.
Lecture--The mechanical equivalent of heat

Joule's Heat Apparatus, 1845, Joule's apparatus for measuring the mechanical equivalent of heat

Further experiments and measurements by Joule led him to estimate the mechanical equivalent of
heat as 838 ftlbf of work to raise the temperature of a pound of water by one degree Fahrenheit.
He announced his results at a meeting of the chemical section of the British Association for the
Advancement of Science in Cork in 1843 and was met by silence.
Joule was undaunted and started to seek a purely mechanical demonstration of the conversion of
work into heat. By forcing water through a perforated cylinder, he was able to measure the slight
viscous heating of the fluid. He obtained a mechanical equivalent of 770 ftlbf/Btu (4.14 J/cal). The
fact that the values obtained both by electrical and purely mechanical means were in agreement to
at least one order of magnitude was, to Joule, compelling evidence of the reality of the
convertibility of work into heat.
Joule now tried a third route. He measured the heat generated against the work done in
compressing a gas. He obtained a mechanical equivalent of 823 ftlbf/Btu (4.43 J/cal). In 1845,
Joule read his paper On the mechanical equivalent of heat to the British Association meeting in
Cambridge. In this work, he reported his best-known experiment, involving the use of a falling
weight to spin a paddle-wheel in an insulated barrel of water, whose increased temperature he
measured. He now estimated a mechanical equivalent of 819 ftlbf/Btu (4.41 J/cal).
In 1850, Joule published a refined measurement of 772.692 ftlbf/Btu (4.159 J/cal), closer to
twentieth century estimates.

An important contribution had C.Miculescu, a Romanian physicist who established


the value of mechanical equivalent of the calory : 1kcal=4185,7 J, a value very close
to the closest value 1kcal=4185,5 J.
2.1.Internal Energy
The first law of thermodynamics represents the energy conservation and
transformation law applied to thermodynamics processes in which energy change is
done as heat and work variation. First law is based on a state measure called internal
energy.
A body, which in thermodynamics is called thermodynamic system, is made of very
high, but finite number of particles in continuous, disordered motion, which interact
amongst them. It means that the particles have a kinetic energy corresponding to
thermal, disordered motion and a potential energy due to forces of interaction
between them (intermoleculare forces) and due to interaction with other external
forces ( ex. gravitational field). All these energies form internal energy of the system.
So internal energy of a system is made of kinetic energies corespunding to particle
macroscopic motions aswell as potential energy of interaction of particles.
Internal energy represents the sum of kinetic and potential energies of the particles
within a body and of the energies within the molecules (ex. energy of chemical
bonds, inter and intra atomic).The last energy,although is contained in internal
energy,does not change during thermodynamic processes because it is not changed
the structure of the body.That is why it is of interest only the variation of internal
energy due to kinetic and potential energy.Internal energy is noted with U and for
thermodynamic processes is the sum of kinetic and potential energy of molecules.

U U cin U pot
U cin U cintrasition U cin rotation U cin oscillatio n

Molecules of liquid and gas may have translation and rotation motions; in the
molecules the groups of atoms have oscilation motions.
For example, internal energy of a gas enclosed in a vessel is composed of : kynetic
energy of translation and rotation of gas molecules; potential energy of molecules
depending on molecular interaction forces; kinetic and potential energies
corresponding to atom oscilation within molecules;electron energy from atoms;
motion and interaction energy of particles which compose the nucleus of atoms.The
last two forms of energy are contained in intermolecular energy E0.
Internal energy U J , kcalis a state measure or quantity meaning that it depends only
by the state of the system. When a system passes from a state having U1internal
energy to another state having U2internal energy, no matter if the process is reversible
or not, variation U=U2-U1of internal energy does not depend on intermediate states
throgh which the system passed,it depends only on the initial and final states ( their
internal energies).Internal energy is an additive measure meaning that the internal
energy of a system is equal to the sum of energies of the components.The ratio of
internal energy to the mass od the system is called specific internal energy and is
noted with u.
m kg

U mu u J / kg

2.2.Enouncements of first law of thermodynamics


On the basis of law there was the experimental observation that mechanic work can
be in heat and reversed.Transformation of the work in heat are met at most friction
processes between bodies, at gas compression and expasion, when work is
transformed in electric energy and then into heat.
a) Heat could be obtained from work and it can be transformed into work always in
the same equivalence ratio.
If in thermodynamic relationships appear heat expressed in kcal and work expressed
in Jouli or kgfm,in order to have homogeneus formula it must expressed the ratio
beween heat and work as the caloric equivalent of unit for work A
Q/L=A , A-caloric equivalent of unit for work.
1kcal 426,86 427 kgf m
1 kcal
A
427 kgfm
If Qkcal Lkgfm
Q AL in technical system

b) It can not be produced a heat engine in continuos operation to produce work L,


without consuming an equivalent quantity of heatQ.

c) Oswald:
Perpetual motion machine of the first kind does not exist.A perpetual motion
machine of the first kind is a machine which produces more work L than equivalent
heat Q,thus meaning it produces energy from nothing; in this way,it violates the law
of conservation of energy.
In a thermodynamic process the variation of internal energy of the system equals the
sum of mechanic equivalents of all energy changes between the system and
surroundings.Any form of energy can be expressed through mechanical equivalent,J.
2.3. Mathematical formulation of first law for open systems
An open system is a thermodynamic system changing energy and mass with the
surroundings.
For a heat engine (a device that converts heat energy into mechanical energy or more
exactly a system which operates continuously and only heat and work may pass
across its boundaries) is expressed the energy balance of the system for period of
time, meaning the balance energy transfer forms and mechanical and thermal
energies.
Q 1-2

L t1-2
2

w1

Heat engine

h1

w2

h2

Reference plan
Fig.4.Scheme of energy changes in a heat engine
It is consider a heat engine from fig. 4 in which point 1 represents the intake of
thermal agent and point 2 represents the exhaust of thermal agent .The heat engine is
supplied by fuel which is burned releasing heat Q1-2; the heat engine produced shaft
work noted Lt1-2. The thermal agent in point 1 has pressure p1,temperature T1, specific
volume v1 , specific internal energy u1and specific enthalpy i1and it gets into the
engine withw1velocity level difference h1.

The thermal agent in point 2 has pressure p2, temperature T2, specific volume v2 ,
specific internal energy u2i specific enthalpy i2and it gets out engine
withw2velocity at a a level difference h2.
Masic balance equation written between points 1 and 2 indicates mass conservation
m1=m2= m .
Energy balance equation written on the control area between points 1 and 2 is:
E1 Ereceived E2 Ereleased

For a time interval


mw12
mgh1 mu 1 J
2
mw 22
E2
mgh2 mu 2 J
2
E1

Ereceived Q12 p1V1

V1 mv 1 m 3

Ereleased Lt p2V2

V2 mv 2 m 3

p2V2 - flow work

Replacing in energy balance:


mw12
mw 22
mgh1 mu 1 Q1 2 p1V1
mgh 2 mu 2 Lt p 2V2
2
2

Q1 2 J

q1 2
m kg

l Lt J
t m kg

Replacing in energy balancefor 1 kgof thermal agent passing through the engine
u2 u1

w22 w12
g h2 h1 p2v2 p1v1 q12 lt
2

J

kg

w22 w12
g h2 h1 q12 lt
2
In which i u pv

1) i2 i1

Diferentiating it is obtained
w2
g dh q12 lt
2

1) di d

J

kg

In which lt vdp
1

Relation 1)has a general character and can be applied in any open system having L
and Q as forms of energy transfer.The second equation is true for mechanical energy
transfers (pumps, etc.).
2.4.Mathematical formulation of first law for closed systems

A closed system is a system which do not change mass with the surroundings,for
example the gas from the cylinder of a piston engine.For equations (1) and (1) from
aforementioned chapter for open systems,considering intake and exhaust velocities
zero and the same value of reference levels.
w1 w2 0

h1 h2
u2 u1 p2 v2 p1v1 q12 lt

It is obtained
2

u 2 u1 q12 vdp d pv
1

1
2

3) u 2 u1 q12 pdV q12 l12


1

Or for m kilos of thermal agent


U 2 U 1 Q12 L12

From 1 (2) i2 i1 q12 lt


2

and I 2 I1 Q12 Lt J for m kilos of agent in which Lt Vdp J .


1

The mathematical expressions in differential


thermodynamics:
du q pdv
pentru 1 kg and
di

vdp

4)

form of the first law of

dU Q pdV
pentru m kg

dI Q Vdp

The mathematical expression of the first law of thermodynamicsfor closed systems


U 2 U 1 Q12 L12 J

favorizes the following hydraulic interpretation and analogy.

U
Q 1-2
L 1-2

Fig.5. Hydraulic analogy of first law for close systems


The analogy emphasizes that internal energy of the thermal agent varies in function
of value and sign of heat and work agent changes with the surroundings.
Special cases :

A.For adiabatic processes Q12 0 the first law becomes a relation between U and
L.When system does not receive energy from exterior, meaning that is adiabatically
isolated, then it could perform work only on the variation of internal energy, Q=0
resultingL = -dU and in this situation work does not depend on intermediate states,
meaning that in this particular situation work is a total diferential (dL=-dU).
B. For isochoric processes (V = ct.) with variation of volume zero,work of the
isochoric transformation is zero Liz 0 and first law becomes a relation between U
and Q.If the system does not perform work upon exterior and exterior does not
perform work upon the system, the heat received by the system from exterior
determines an increase of its internal energy and L=pdV=0 and dQ = dU or
Q1-2 = U2 - U1 .
In the isochoric process the heat is a total differential.
C.When
Q12 0 the.agent .receives .heat

L12 0 the.agent . peforms .work U cons tan t (isothermal . process )


Q L
12
12

When agent receives heat and performs work, if these quantities are equal,internal
energy remains constant.
In other words when internal energy does not change during its interaction with
the environment, then system cannot perform work unless it receives energy from
exterior.For dU=0,it is obtainedL = Q or Q1-2 = L1-2.
2.5 Caloric equation of state
The quantities intenal energy U and enthalpyIare called caloric state quantities
reprezenting thermal forms of energy.
Rule The state of thermal equilibrium of a system is completely determined if are
known two intensive state parameters and masses mj of components of the system.
Intensive parameters are pressure, temperature,specific volume.
It is considered a monocomponent system (1 body ), having mass of 1 kgfor which
any state quantity can be expressed in function of two intensive parameters.
u f T , v
It is expressed:
.By differentiation
i f1 T , p

u
u
du T dT v dv

v
T

d i i dT i dp
p

T p
T

For 1 kilo of agent which suffers an elementar heating at constant volume:

q v

cv dT

According to first law for closed systems:


du q pdV for v cons tan t du v q v and du v cv dT

U f t , v
U
cv

T v

Similarly results :
i
cp
T p

Replacing in duand di results

u
du cv dT v dv
T

d i c dT i dp
p
p

analog with capital letters for m kg :

U
dU mcv dT v dV

d I mc dT I dp
p
p

These equations are called caloric equations of state.


Questions
1. Is the work performed by a system a form of energy exchange ?What about the
heat change ?
2. Can be mechanic work converted into heat ? Can be heat converted into work?
3. What are units for work and heat ?
4. What is internal energy of a system ?
5. Which is the enouncement of the first law of thermodynamics ?
6. Which is the enouncement of the first law of thermodynamics for closed
systems?
7. Which is the hydraulic analogy of the first law of thermodynamics for closed
systems ?
8. Which are the caloric equations of state?

Chapter 3. The ideal gas


Ideal gas is a hypotetic notion - it represents a gaseous body having the following
properties:
- molecules are perfectly spherical;
- molecules are perfectly elastic;
- molecules have nointeraction;
- molecules own volume can be neglected;
The perfect gas is also called ideal gas and, according to the kineticmoleculartheory,
it cannot be liquefied.
Relations expressing the properties of a perfectgas are:
a) the expression of a gas pressure (Bernoulli)
2 N mw 2
p
3V 2

b) the expression of kinetic energy Ecas a function of the velocity distributionw


3
mw 2
kT
2
2

(Maxwell Boltzmann)
m molecule mass
N number of molecules in V

Out of the two relations, pV kNT , where k 1,38 .10 26 -the Boltzmann constant
For a constant mass of gas (N = constant)it results :
pV
constant - the ecuation of state for a hypotetical perfect gas.
T

In certain pressure and temperature conditions, gases in nature almost obey the
rigurousrelations for the hypotetical perfect gas: these generic conditions consist of
small and medium pressures and medium and high temperatures so states that are
far enough from the liquefying point.
Gases in the nature that are in such conditions can be considered perfect gases; the
simple laws established in XVII-XIXcenturies that are not rigurously correct were
determined by experiments on gaseous bodies in the nature, in pressure and
temperature conditions far away of liquid states, thus obtaining the laws of perfect
gases. The approximation of the simple laws of gases is sometimes under the errors
introduced by mathematical models of the phenomena.
3.1.Laws of the perfect gas
For a constant mass (kg) of perfect gas, these laws are as follows:
a) Thermal state equation

pV
ct or pV mRT
T

- the variables are expressed in different measurement units:


pV
pV

pV
pV

RT
mRT

1kg
mkg

nRM T

nkmol

RM T

1kmol

R is called the constant of the gas. Its value doesnt depend on its status, but only on
its nature and thermal properties.
For a kmol of gas, the state equation becomes:
pvM MRT
pVM RM T

, where RM is the the universal constant of the perfect gas, being

independent of the natureof the gas and having a value that can be computed out of
the state equation of the gas in normal physical conditions.
R
101325 22.414
J
8314.4 J
and R M
8314.4
kg.K
TN
273.15
kmolK
M
M

3
m
N
T K ,
p 2 , V m 3 , v
m
kg

RM

p N VMN

J
m kg, nkmol R

kgK

b)Boyle Mariotte law


When T constantthen pV constant
c) Gay Lussac law
When p constant

then

V
constant
T

d) Charles law
When V constant then

p
constant
T

e) Avogadro law(1811)
At the same pressure p and temperature T, in equalvolumesthey are the same numbers
of molecules.

For gases 1 and 2 :


p1 p 2 T1 T2 V1 V2 N 1 N 2

- numbers of molecules

1 kmol contains NA= 6.023 1026 molecules


1 kmol 22 .414 m N3

In normalstate, 1 kmol occupies the same volumeV.


f) Joule law
Internal energy of perfect gases depends only on temperature.
U U T

U
U
0
0 (independence on p or V)
V
p

and

Entalpyof perfect gases depends only on T.


I U pV U mRT I f1 T

Consequences:
- general expressions of caloric state equations:
U
dU mc v dT
dV
V T

I
dI mc p dT dp
p T

For the perfect gases:


U

0 according to Joule law


V

0 according to Joule law.


p

We obtain the following expressions of the caloric state equations for perfect gases:
dU mcv dT

dI mc p dT

For 1 kg
du cv dT

di c p dT

and, integrated,
U 2 U 1 mcvm T2 T1
J

I 2 I 1 mc pm T2 T1

3.2.Specific heat of perfect gases


The ratio of specific heats is calledadiabaticexponent and is noted as:
cp
cv

c Mp
c Mv

C Np
C Nv

cM Mc

c M 22 .414 C N

It can also be written i u pv u RT and, in diferential form,


di du RdT or c p dT cv dT RdT

J
- Mayer relation
c p cv R
kgK

J
Mc p Mcv MR or cM p cM v RM
RM RM
kmolK

J
R
cv

cp

k 1 kgK
k

cv
c c R
c k R J
p v
p k 1 kgK

RM J
cMv k 1 kmolK

c k R J
Mp k 1 M kmolK

One can notice that specific heats of perfectgas can be determined as a function of
adiabatic exponent k and of the constants of the gas.
For the hypotetic perfect gas, specific heats areconsidered constant and k = constant.
Specific heats of gases considered as perfectcan vary with temperature.Experiments
show that, for these gases, kstaysconstant in large intervals of temperature. For first
approximation computation, the following values are adopted:
- for monoatomic gases (He),k = 1.66
- for biatomic gases(N2, O2, H2, CO),k = 1.4
- for polyatomic gases(CO2, SO2.),k = 1.33
The hypotetic perfect gaswith punctiform moleculesbehave like a monoatomic gas,
with c constant and k constant. For gases of the nature with two or more atoms in the
molecule, the degrees of freedom in molecules movement appear progressively with
the increase of temperature.
- for low temperatures only translation
- for medium temperatures (e.g. atmospheric temperature) translation + rotation
- for high temperaturestranslation + rotation+ oscillation.

As a consequence of progressing in rotation and, then, in oscillationof molecules


atoms, specific heats increase with temperature. For termotechnical computation, in
the first approximation, for biatomic gas the adopted value isk = 1.4.
3.3 Real gases
The differences between ideal and real gas can be described as follows:
- a gas behaves like an ideal gas when it is very rarefied in this case, the own
volume of molecules versus the whole volume occupied by the gas can be
neglected and molecular interraction forces are very low due to large distances
between molecules.
- a gas behaves like a real gas at high pressures and low temperatures, when neither
own molecules volume nor molecular interraction forces can be neglected.
The status equation for a kilomol ideal gas, pv = RT , becomes for the real gas:
a

p 2 v b RT , (Van de Waalsequation), wher a and b aretwo constants.


v

The real gas is different from the ideal gas (whose internal energy depends only on
temperature), as the internal energy of the real gas dependsalso on volume, so
U = U(T) - for the ideal gas
U = U(T, V) - for the real gas
In ideal gases, molecules dont interract and internal energy consists only of the
kinetic energy of the molecules, that depends only on the temperature of the gas. The
internal energy of the real gasconsists of the kinetic energy and potentialenergy of the
molecules, due to their interraction the potentialenergy depends on the distance
between molecules, so, on the volume of the gas.
3.4. Mixtures of perfect gases
In most installations, the gaseous thermal agents are not pure gases, but mixtures of
gases.
Examples:
- the air is a mixture of gases, mainly N 2 O2
- exhaust gases consist of CO2 H 2 Ovap SO2 O2 N 2 CO.....
A mixture of perfect gases behave like a perfect gas:
pV mRT

For the study of gaseous mixtures, they are two hypoteses:


a) mixed gases - molecules of each gas spread in whole the volume.
A B C A A
B C A B C
B
B C B A
A B
C A
B C C
A
C
B
C
A
B
C
A
C
C B C
A
B C
A
C
B
B A
B
C
A
B
B
C
A
A
B
B
C
A
A
C B
B
C

Fig.6. Mixture of molecules in the whole volume


Given three different gases, A, B and C, with molecules of different sizes, it can be
considered that they occupy all the available volume:
V A VB VC V

Temperature of the components can be considered as equal with that of the mixture:
T A TB TC T

Partial pressure is the pressure of a gas on the enclosure walls if it should be


alone.For the chosen three gases, partial pressures are not equal:
p A p B pC - partial pressures
The pressure of the mixture is the sum of the partial pressures of component
gases: p A p B pC p - Daltons law
The sum of component masses is the mass of the mixture:
m m A mB mC kg

They are called mass fractions (concentrations) the ratios:


m
gA A
m

gB

mB
m

gC

mC
m

b) component gases are separated by imaginary walls, each having the same
pressure p and temperature Tas the mixture.

A A
A

A
A A A

B B
B B
B B
B B B
B
B

C C
C
C
C C
C
C
C C C
C

B B

Fig.7.Mixture of molecules in partial (imaginary) volumes

For this hypothesis


p A pB pC p
T A TB TC T
V A V B VC

The partial volumes of the components are different because the partial enclosures
are different.
The sum of the partial volumes of the components is equal to the volume of the
mixture.
VA VB VC V

- Amagat law

There are called volumic fractions the ratios


rA

VA
V

rB

VB
V

rC

VC
V

i ri 1

Properties of ideal gas mixtures


1. Constant R of the mixture .
It is considered the mixture made of gases A,B and C in conditions described in
paragraph a). For every component it can be written the equation of state:
p AV m A R AT
p BV m B RB T
pCV mC RC T

Summing the equations, it results:


pV m A R A m B RB mC RC T

pV mRT equation of state of the mixture


mR m A R A m B RB mC RC and dividing by m, it results
R

n
mA
m
m
RA B RB C RC g A RA g B RB gC RC gi Ri
m
m
m
i

R constant of the mixture is equal to he sum of the gas constants of the components,
weighted with the mass fractions.
2.Specific mass of the mixture

m
(density)
V

Considering the hypothesis from paragraph b, it can be written


m m A m B mC AV A BVB CVC and dividing to volume V
rA A rB B rC C

i i

Density of a mixture is equal to the sum of gas densities weighted with the volume
fractions.

3.Specific volume of the mixture v

V Vi mi vi

g i vi
m
m
m
RT
in which vi i are specific volumes of the components.
p
v

4. Molar mass (weight) of the mixture M


Molar mass (weight) of the mixture is called conventional mass because it does not
have a measurable value in real life. If it is considered the density of the mixture and
components
mi
p
p

i V R T R T M i

i
i
M

ri i in which
i
m p p M

V RT RM T
n
p
p
M ri
M i M ri M i
It results the equality
RM T
RM T
i
n

Molar mass of the mixture M equals the sum of molar masses of the components
weighted to volume fractions.
5.Partial pressures of the gas components
For component i it is expressed the equations of state which correspond to both
hypothesis of the mixtures which are considered to be equal:
piV mi Ri T
p Vi mi RiT

pi

Vi
p ri p
V

The partial pressure of a component is qual to the pressure of the mixture p weighted
with the volume fraction of the component ri.
For example, for air at atmospheric pressure considered close to 1 bar:

p N 2 0.79 bar

pO2 0.21 bar

6.Specific heat of the mixture


It is considered a mixture which suffers an elementary heating process at constant
pressure or volume;heat change is expressed
Q mcdt in which specific heat c is either cp or cv.
Heat received by the mixture equals the sum of the heats received by every
component.

Qi mi ci dt
n
n
m
c i ci g i ci
i m
i

Similarly, it can be demonstrated that

ri cMi

cM
CN

r C
i

Ni

7.Conversion of the fractions


The mixture composition is expressed through mass or volume fractions.
By definition : g i

mi
mi

m
mi

- In hypothesis b) pVi mi Ri T mi

RM
T
Mi

gi

gi

Vi M i
RM T
1
p
V
Vi M i
RM T
ri M i

r M
i

By definition : ri

ri

ri

Vi
V
i
V
Vi

RM T mi
p Mi 1
RM T mi m
p Mi
gi
Mi
gi
Mi

rO 21% gO 23%
Example for air:
2

rN 2 79% g N 2 77%

g O2

ro 2 M o 2
0.21x32

0.23
ro 2 M o 2 rN 2 M N 2 0.21x32 0.79 x 28

g N2

rN 2 M N 2
0.79 x 28

0.77
ro 2 M o 2 rN 2 M N 2 0.21x32 0.79 x 28

8. Mean temperature of a mixture


There are considered several gases initially at different temperatures and it is required
the final temperature of the mixture, after mixing process. Fom equation of heat
balance considering that a component releases heat and the others absorb heat :
m1c1 T1 T m2c2 T T2 m3c3 T T3

The temperature of the mixture is T


T

m1c1T1 m2 c2T2 m3c3T3

m1c1 m2 c2 m3c3

m c T
m c

i i i
i i

Chapter 3. The ideal gas (continued)

3.5.Thermodynamic processes applied to the ideal gas


When a heat engine is designed, the real processes of heating, cooling, compressing
and expanding are replaced with one or more simple thermodynamic processes or
transformations.
- The thermodynamic process which takes place at constant volume is called
isochoric transformation (V = constant)
- The thermodynamic process which takes place at constant pressure is called
isobaric transformation (p = constant)
- The thermodynamic process which takes place at constant temperature is called
isothermal transformation (T = constant)
- The thermodynamic process which takes place without heat exchange with the
surroundings is called adiabatic transformation (Q =0)
- The thermodynamic process which takes place with variation of all parameters of
state, in the condition of a constant specific heat of the process (cn =constant) is
called polytropic transformation.
For each type of transformation it is necessary to know the equation of the
transformation ( relation between the parameters of state in initial and final points) ,
mechanic work variation , heat exchange and graphical representation, typically in pV coordinates.
3.5.1. Isochoric transformation
The isochoric transformation takes place at constant volume V= constant ,
pV
cons tan t
T
p
T
p
cons tan t (equation of the transformation ) or 2 2
p1 T1
T

( m cons tant ), from equation of state

it results if V is constant

The mechanical work of the isochoric transformation is


2

L12 L pdV 0 as V cons tan t


2

T2

T1

Heat transfer of the isochoric transformation is Q12 Q mcv dt mcv T2 T1


m

Caloric equations of state :

U 2 U1 mc v m T2 T1 Q12
I 2 I1 mc pm T2 T1

Graphical representation of the transformation in p-Vcoordinates is like in fig. 8,


where the transition from state 1 to state 2 is characterised by keeping the volume
constant: V1 V2 V
p
2

Heating

Cooling

p2

p1
1

V
Fig. 8. Plot of the isochoric transformation in p-V coordinates
As the p/Tratio stays constant with pressure increase, e.g. passing from state 1 to state
2 (p2>p1), the temperature would increase, (T2>T1) resulting a heating of the gas. If
the process inverts, from state 2 to state 1, the gas would cool as the pressure
decreases.
The physical model of a thermodynamic system undergoing such a transformation is
that of a fluid container with fixed exterior walls. Heating by an external source gives
an increase of the temperature and of the pressure in the container.

3.5.2.The isobarictransform
The isobaric transformis characterized by a constant pressure, p= constant ,
pV
cons tan t . It results, for p constant,
T
V
T
V
cons tan t (the equation of the transformation) and 2 2
V1 T1
T

( m cons tant ), inthe state equation

Mechanical work of the isobaric transformis:


2

L12 L
1

pdV p dV

L12 pV2 V1 J

Heat exchange of the isobaric transformwith the external environment is


2

Q12 Q mc p dT
1

Q1 2 mc pm T2 T1 J

For heating, Q 0 , L 0
For cooling, Q0 , L0
Modification of caloric state variables:
U 2 U 1 mc vm T2 T1 J

I 2 I 1 mc pm T2 T1 Q1 2

Graphical representation of the transformation in p-V coordinates is like in fig. 9,


where the transition from state 1 to state 2 is characterised by keeping the pressure
constant: p1 p2 p
p

Heating
p

Cooling

V1

V2

Fig. 9. Plot of the isobaric transformation in p-V coordinates


As the V/T ratio stays constant with volume increase, e.g. passing from state 1 to
state 2 (V2>V1), the temperature would increase, ( T2>T1 ) resulting a heating of the
gas. If the process inverts, from state 2 to state 1, as the volume decreases, the gas is
cooling.
The physical model of a thermodynamic system undergoing such a transformation is
that of a fluid container with a mobile exterior wall pushed by a constant force that
gives a constant pressure. Heating by an external source gives an increase of the
temperature and of the volume occupied by the gas.
3.5.3. Isothermal transformation
Theisothermal transformationtakes place at constant temperatureT= constant,
pV
cons tan t it results if T is constant
T
pV cons tan t (equation of the transformation ) or p1V1 p2V2

( m cons tant ), from equation of state

The mechanical work of the isothermal transformation is:

L12 L
1

where pV cons tan t p1V1 p2V2

L12

pdV

V
dV
dV
ct
p1V1
p1V1 ln 2
V
V
V1
1
1

L12 p1V1 ln

V2
p
V
p
p1V1 ln 1 mRT ln 2 mRT ln 1
V1
p2
V1
p2

Heat exchange of the isothermal transformation is :


Q mcdT

Q 0

dT 0

The isothermalprocess has a specific heat of . In order to solve such an


undetermination, the general formulas of the 1st principle are used:
dU Q pdV Q L L pdV

dI Q Vdp Q Lt Lt Vdp

and, using the caloric state equations for the perfect gas:
dU mcv dT

dI mc p dT

dU 0
or Q12 L12 J
Q L

it results, for T cons tan t

Only in the isothermal transformation, Qexchanged by the agent with the


environment is equivalent with the mechanicalwork done or consumed by the
thermal agent during the transformation.
Q12 p1V1 ln

V2
p
V
p
p1V1 ln 1 mRT ln 2 mRT ln 1
V1
p2
V1
p2

Graphical representation of the transformation in p-V coordinates is like in fig. 10,


where the transition from state 1 to state 2 is characterised by keeping the product
pVconstant.
p
p1

Expansion

p2
Compression
V1

V2

Fig. 10. Plot of the isothermal transformation in p-V coordinates

The plot is an equilateral hyperbole arch.


In the isothermal transformation:
U 2 U 1 mc vm T2 T1 0
I 2 I1 mc pm T2 T1 0

The physical model of a thermodynamic system undergoing such a transformation is


that of an engines cylinder that is intensely exchanging heat with the environment.
When the piston moves, the decrease of volume gives an increase of pressure so the
temperature tends to increase as well. Assuming that cylinders walls allow the
release of a heat thats large-enough, it can result a constant temperature of the gas in
the cylinder.

3.5.4.Adiabatic transformation
The adiabatic transformation is the thermodynamic transformation without any heat
exchange with the external environment Q 0 Q12 0
Parameters p, T, V are variable and the goal is to find their relationship under these
conditions
dU Q pdV
dI Q Vdp
dU mcv dT
Caloric equations of state:
dI mc p dT

1st principle:

Replacing dU, dI and computing the ratio, it gives:


cp
cv

c
Vdp
where p k
cv
pdV

k is the adiabaticexponent that represents the ratio of specific heats of a gas n the
isobaric respectively in the isochoric transformation.
Integrating the

dp
dV
k
0 equation gives
p
V

ln p ln V cons tan t that leads to the


k

equation of the transformation in p and V coordinates:


pV k cons tan t
or p1V1k p2V2 k
Logarithmation and differentiation is applied to the state equation, in the form
pV
cons tan t .
T
dp dV dT
p V T
dT
dV

k 1
It results
0
T
V
dp k dV 0
p
V

that, after integration, gives the equation of the adiabatic transform with parametersT
and V:
TV k 1 cons tan t

T1V1k 1 T2V2k 1

ReplacingVgives

k 1
k

T p
cons tan t or 2 2
T1 p1

k 1
k

that represents the equation of the

adiabatic transform with p and T.


The mechanical work of the adiabatic transform is:
2

L12 L
1

pdV
1

L12

where pV k cons tan t p1V1k p2V2k

dV
ct k ct V k dV
V
1
1

ct

V2k 1 V1k 1
k 1
the constant is replaced with p2V2k and then with p1V1k .
L12

p1V1 p2V2
mRT1 T2 mRT1 T2
or L12

1
k 1
k 1
k 1 T1
k 1

p1V1 p2 k
L12
1
k 1 p1

The heat exchange of the adiabatic transform is Q 0 Q12 0 , that means that for
L12

this transformation, the specific heat is zero: c ad 0 .


Variation of caloric state variables:

U 2 U1 mcvm T2 T1
where L12 U1 U 2 J Lt I1 I 2

mc
T

T
2
1
pm
2
1

pV k cons tan t

Graphical representation of the transformation in p-V coordinates is like in fig. 11,


where the transition from state 1 to state 2 is characterised by keeping the constant
product: V1 V2 V
p
p1

Expansion

p2
Compression
V1

V2

Fig. 11. Plot of the adiabatic transformation in p-V coordinates


The plot is a hyperbole arch with greater slope than the equilateral hyperbole, as the
values k> 1.
The physical model of a thermodynamic system undergoing such a transformation is
that of an engines cylinder with a perfectly thermal isolation, that doesnt allow any
heat exchange with the environment.
3.5.5.The polytropic transform
The polytropic transform is a general transformation in whichp,T,V vary and energy
is exchanged in form of Q and L with environment .
The polytropic transform is a process in which all parameters vary, so in order to
define the transformation it is accepted that the specific heat is given and constant
c n .
cn = polytropic specific heat
Q mc n dT

To find out the equation of the trasformation:


dU Q pdV
with
dI Q Vdp

First law

dU mcvdT
Q mc n dT

dI mc p dT

c c
c c
mc p dT mcn dT Vdp
Vdp
Ratio p n
is noted with n p n and is called

cv c n
pdV
cv c n
mcv dT mcn dT pdV

polytropic exponent. It is considered that ratio constant (n=constant )during a


polytropic transform.
dp
dV
n
0
p
V

pV n cons tan t - equation of

p1V1 p2V2

the transformation in p,V

dp dV dT dp ndV
dT
dV
n 1

0
;

0

T
p
V
T
V
p V
TV n1 cons tan t
-equation of the transformation in T,V or T1V1n1 T2V2n1
T
n 1
p n

p
T
-equation of the transformation in T,p or 2 2
T1 p1

cons tan t

The work of the polytropic transform is L12 L pdV


n

p1V1n

pV ct
2

L12 ct

p 2V2n

p 2V2 p1V1
dV
ct
n
n 1
n 1

ct
V
dV

2
1
n 1
n 1
Vn
1
1

n 1
n

or

p1V1 p 2V2
n 1
mRT1 T2 mRT1 T2

1
n 1
n 1 T1
n 1

p1V1 p 2 n

1
n 1 p1

L12
L12

L1 2

The heat exchange of polytropic transformis:


Q mc n dT
2

Q12 Q mcn dT mcnm T2 T1

Considering n constant, as known, for o given polytropic transform, it can be deduced


cnfrom ratio n

c p cn

cn

ncv c p

cu

cp
k
cv

cv c n
n 1
nk
Q mcn dT m
cv dT
n 1
nk
Q12 mcnm T2 T1 m
cvm T2 T1
n 1
It is usual to express Q12 in function of Lmec
dU Q L
dL
dU
mc dT
n 1 k 1
1
1 v
1

Q
Q
mc n dT
nk
nk
k n
k n
Q
L , iar Q12
L12
k 1
k 1

cn

nk
cv
n 1

The caloric state quantities of polytropic transform are:


U 2 U 1 mcvm T2 T1
J

I 2 I1 mc pm T2 T1

Giving to n values in the interval ( , )it can be obtained an infinity of polytropic


transform; not all corespond to heat engine processes.
Experimentally it was determined that:
1)
The compression and expansion processes form heat engines are accompanied
by heat exchange of the agent to the environment; this heat exchange is not so intense
to reach an isothermal process.
2)
During realcompression and expansion processes the heat exchange with the
environment cannot be completely avoided and these processes do not undertake
perfectly adiabatic.
Conclusions : Real compression and expansion processes can be considered as
polytropic processes situated between isothermal and adiabatic transformation.
From the equation of realpolytropic transform pV n cons tan t
n 1 pV ct isothermal
n k pV k ct adiabate

So in thermodynamic calculation it is of interest the study of


transformation having n complying with the inequation 1 n k ,in which
k=1.33...1.6.The graphic of the transform versus n values is :

polytropic

2iz
2ad

2pol

V
p

2iz

2pol

2ad

V
Fig.12.Reprezentation of polytropic expansion and compression in coordinate p-V
Observations:
Giving particular values to n the simple transformations can be deduced from
polytropic transformation.
a) n 1
b) n k
c) n 0

nk
cv ciz
n 1
nk
pV n ct pV k ct
cn
cv cad 0
n 1
nk
pV n ct p ct izobar cn
cv c p kcv
n 1

pV n ct pV ct

cn

d) n pV n ct p n V ct V ct izocor c n c v
The specific heats for different polytropic transformation can be obtained according
to n values from diagram.

cn
cp

cv
0

Fig.13.Specific polytropic heat versus polytropic exponent


The polytropic curves in function of n if it isconsidered that all curves pass through a
given point.
a) n = 0
p = ct
b) n = 1
T = ct
c) n = k
adiabatic
d) n = V = ct
e) n = -1
f) -<n<-1
g) -1<n<0
h) 1<n<k

1-1
2-2
3-3
4-4
5-5
6-6 between (4-4, 5-5)
7-7 between (5-5, 1-1)
8-8between (2-2, 3-3)
3

p
7
1

2
8
3
7

4
6

Fig.14. Polytropic curves in the hypothesis that pass through a given point.

Fromthe point of view of the heat exchange the adiabatic splits the p-Varea in two
zones in any transformation which starts from a point of the adiabatic and
undertakes upwards the adiabatic, in zone I, the heat exchange is positive.
2

5 3

4
I

II

5
3
4

Fig.15.The zones of the heat exchange defined by adiabatic curve


I Q 0

- example: A4 A 1, A2, A5

In any transformation which starts from A and undertakes under adiabatic curve 3-3
(zone II) the heat exchange is negative.
II Q0

- example: A4, A-1, A2,A5.

Questions
1.
2.

Which are the hypothesis of the ideal gas ?


Which is the equation of state of ideal gas?What is the meaning of the
quantities used?
3. What are the laws of ideal gas ?
4. How is defined the adiabatic exponent k ?
5. Which is Mayersequations?
6. What is the equation of real gas ? In what conditions the real gas is close to
ideal gas ?
7. Which are the hypothesis to gas mixture?
8. What is Dalton law? What is Amagatlaw?
9. What is a simple transformation?Which are the simple transformations of
ideal gas ?
10. Which is the equation of isochoric transformation ?Which is its
representation in p-V ?
11. Which is the equation of isobaric transformation ? Which is its
representation in p-V ?

12. Which is the equation of isothermal transformation ? Which is its


representation in p-V ?
13. Which is the equation of adiabatic transformation ? Which is its
representation in p-V ?
14. Which is the equation of polytropic transformation ? Which is its
representation in p-V ?
15. How is defined the polytropic exponent ?

Course 6
Chapter 4. Second law of thermodynamics
4.1. Thermodynamic cycles
It is called thermodynamic cycle (or a cyclic thermodynamic process) aseries of
succesive thermodynamic processes (or transformations) which undertake in such a
way that at the end of last transformation the thermal agent is brought in the initial
state of the first transformation.
If it is considered the cycle 1A2B1,
p
A

Lc

Fig.16. The thermodynamic cycle in coordinates p-V


It is called the work of the cycle the sum of all works (Lc =
transformations which compose the cycle.
1

Lc L
1

Lc

mec

)performed in the

L L

1 A2 B

1 A

2B

L L L

1 A 2

L2 B 1

- in transformation 1-A-2
- in transformation 2-B-1

dV 0 and

L pdV 0 L1A2 0

dV 0 and

L pdV 0 L2B1 0

L1 A2 area1A22 '1

L2 B1 area2B11'2'

Lc L1A2 L2 B1 L1A2 L2 B1 area1A2B1

Considering the sign of work , the cycles are divided in:


a)
Work producing cycles- Lc 0 when cycle is perfomed clock wise, characteristic
to energy producing aggregates, such as internal combustion engines, gas turbines
b)
Work consuming cycles - Lc 0 when cycle is perfomed anti clock wise
(trigonometric), characteristic to energy consuming aggregates such ascompressors,
refrigerating installations.
For an arbitrary cycle the points 1 and 2 are in contact to 2 adiabates.

p
A

Lc

Adiabate II

Adiabate I
1

Fig.17. The cycle placed between two adiabates


For a heat engine working on this cycle,the first law of thermodynamics is expressed:
dU Q pdV Q L

It is applied the formula for the cycle12B1


1) dU Q L
2) dU 0
3) L Lc
4)

1A

2B

Q Q Q
2

In which Q Q1A2 0
1A

The transformation 1A2begins on the first adiabate and undertakes upwards (beyond)
the adiabate.
2

Q Q

2 B1 0

2B

The transformation 2B1 begins on the second adiabate and undertakes downwards
(beneath) the adiabate.
It is noted heat amount received by the agent during the transformations of the
cycleQ, Q 0
It is noted heat amount released by the agent during the transformations of the cycle
Q0, Q0 0

Q Q Q0 or Q Q Q0 Lc Q Q0

In an work producing cycle performed by an ideal gas, only a part of the heat
received by the agent (Q) is transformed in work Lc, the rest of the heat being
released to the environment during the rest of the cycle transformations.
It is called thermodynamic efficiency of the cycle the expression :
t

Q Q0
Q0
Lc
t
1
Q
Q
Q

The efficiency expresses the thermodynamic quality of the cycle.

4.2.Reversible and irreversible processes


As presented in chapter 1.4, the thermodynamic processes can be divided in:

Reversibile process, in which the system passes from initial to final state
directly and reversely,exactly through the same points, on the same path.

In order to perform such a process, the external conditions should modify extremely
slow, so the system to adapt progresively to the new variations which gradually
appears;

Irreversible or non-reversible process, in which the system passes from initial


to final stateand reversed through different points, on other path.

Real processes cannot be considered reversible. A process can be considered


reversible if intermediate states when passing from initial to final state are close
enough to intermediate states when passing from final to initial state.
All thermal and mechanical processes in nature are irreversible,they undertake
naturaly in one way, to a state with higher probability of achievement;the causes of
ireversibility are:
-Processes have finite velocities (not very slow);
-friction during process;
-molecular difusion;
-heat exchange at finite temperature difference;
-finite variation of internal and external conditions.
In order to study real processes from heat engines, all real irreversible processes are
replaced with equivalent reversible processes.
Examples of irreversible processes:
Passing of gas ( on its own,naturally ) from an area of high pressure to an area of
lower pressure and never in reverse way.
At the contact of two bodies of different temperatures, after a period of time,the
bodies reach an intermediate temperature, never happened that hot body to
become hotter and the cold one to become colder, even the first law of
thermodynamics is obeyed.
If two gases ( or a water-sugar solution ) are introduced in the same enclosure the
tendency of the molecules will be to mix, never to separate, no matter how long we
will wait for.
Other irreversibile processes are the errosion of theEarth crust, metal corrosion,
aging of material and people.
4.3.Versions of second law

First law represents the generalization of energy conservation law for thermal
processes and the second law was discovered during experimental research of heat
engines, and its content applies to other energy changes, not only of thermal
nature.The physicists noticed that heat engines cannot transform totally the absorbed
heat in work.The second law asserts the irreversibility of the natural processes
explaining terms of conversion of heat into work Q L and rounds the first law.
First law: Work turns into heat on the same equivalent ratio, meaning L Q and
Q L ,but it does not say anything about the possibility of reverse
transformation,emphasizing just the equivalence.
Second law says the possibility and the sense in which the processes are undertaken.
Work turns into heat L Q
spontaneously, integrally
(on its own-de la
sine).Heat turns into work Q L by means of a heat engine in which irreversible
processes take place and Q L transformation is partial.
The second law says that temperature differences between systems in contact with
each other tend to become equal and work can be produced from non-equilibrium
differences (temperature, pressure and density differences).For an isolated system all
parameters,particularly temperature will eventually have constant,uniform values. A
heat engine is a mechanical device that provides useful work from the difference in
temperature of two
Hot
source

bodies:

Heat
engine

Q0

Cold
sink

Since any thermodynamic engine requires such a temperature difference, it


follows that no useful work can be derived from an isolated system in equilibrium;
there must always be an external energy source (hot source or heat reservoir ) and a
cold source (sink).So,second law shows that work can be totally turned into heat, the
inverse transformation is not correct, heat cannot be totally turned into work.The
cause of the assymetry is the fact that work corresponds to a ordered motion of
particles and heat corresponds to a disordered one.Second law has many formulations
of the physicists who studied thermodynamics,which are equivalent.
Formulations
a.Clausius:Heat generally cannot spontaneously flow from a material at lower

temperature to a material at higher temperature.(irreversibility of spontaneous


phenomena).

b. It cannot be reversed on the same path ( through the same intermediate states) a
process in which friction generated heat.(irreversibility of processes accompanied by
friction).
c.Clausius: A heat engine running continuously converting to work the heat
absorbed from a hot source without releasing heat to a cold source is impossible.
d. Kelvin:It is impossible to convert heat completely into work.
It is impossible to produce work in the surroundings using a cyclic process
connected to a single heat reservoir.
d.Oswald : Perpetual motion machine of the second kind is impossible.
Perpetual motion machine of the second kind is a machine which runs only with a hot
source.
e. The heat of a hot source cannot be converted into work without producing
changes to environment (heat release to environment ).
f.A thermodynamic system will naturally evoluate from the state with lower
thermodynamic probability to the state with higher thermodynamic probability.
Explanation : To understand the thermodynamic probability it is considered that N
molecules occupy a given volumeand it is surveyed the distribution of the molecules
in two halves of the volume.It is considered that at a given moment, N1 moleculesare
situated in left side and N2in right side.
N1

N2
N N1 N 2

Any change in molecules distribution will lead to a new state regarding system
distribution. A state is defined if it is in equilibrium and there are known some
characteristic quantities: mean kinetic molecular energy,mean potential molecular
energy, molecular distribution in the volume.
Molecules are continuously in motion,changing position and velocity.The distribution
of molecular velocities and positions ( coordinates)in the enclosure at a given
moment determine a micro-state of the system.As a result of a perpetual molecular
motion, the micro-states vary continuously.
At the equilibrium, the macroscopic properties of the system do not vary in time
even at molecular level the microstates change; this is possible because the
thermodynamic properties appear as an mean effect of the processes produced at
molecular level.
p

2 N mw 2 mw 2 3
kT
,
3V 2
2
2

The number of microstates corresponding to an equilibrium state represents the


thermodynamic probability of the equilibrium state. The total number of microstates
determined by the variation (permutation) of velocities and positions, keeping
themean kinetic molecular energy constant represents the thermodynamic probability.
Coming back to the distribution of N moleculeswithin the enclosure,it can be noticed

that, in theory, at molecular level,are possible any kind of distribution (for example
N1 0 N 2 N ); flowing of a molecule from right to left or the change of position of
two molecules determine a new micro-state; applying the thermodynamic
probability,it is noticed that it is possible any distribution between N1and N2, but
every distribution has a different thermodynamic probability.
For a system made of N = 100 molecules,thermodynamic probability P resulted from
N distribution in N1and N2:
P

N!
N1 ! N 2 !

N1
0
10
20
30
40
45
50
N2
100
90
80
70
60
55
50
13
20
25
28
28
P
1
1,6.10
5,25.10
2,8.10
1,31.10
6,65.10
1,12.1029
All the experiments showed that at macroscopic level the molecules will distribute
uniformely N1 N 2 meaning that they reached the state with the highest
thermodynamic probability.
If it is measured in the two halves of the enclosure the pressure and temperature of
gas, at equilibrium, the values are equal.
Although at microscopic level are possible all the distributions, at macroscopic level
is evident the state which corresponds to maximum probability.
Second law says that the thermodynamic processes undergoes in the sense of
reaching the maximum thermodynamic probability.The content of second law is
connected to the microscopic interpretation, being a statistic law.
4.4 Carnot cycle
The most efficient cycle of transformation Q L is the cycle in which the agent gets
in contact to two heat sources; a heat source (thermostat) is a body with constant
temperature having infinite caloric capacity.The cycle is formed of two adiabates and
two isothermes:
1
Q

Lc
4
3
Q0
V

Fig.18. Representation of Carnot cycle (work producing)in p-V coordinates


1-2 isothermal expansion (T = ct), the agent receives heat Q12 Q hot source
2-3 adiabatic expansion Q23 0

3-4 isothermal compression (T0 = ct), the agent released heat Q3 4 Q0 cold source
4 1 adiabatic compression Q41 0
The efficiency of Carnot cycle when the agent is an ideal gas is :
t

Q0
Lc Q Q0
in which Lc Q Q0

1
Q
Q
Q

For Carnot cycle when the agent is an ideal gas it can be written :
V2
V1
V
V4 V3
Q0 Q34 mRT 0 ln 4 in which
V3
V
Q0 mRT 0 ln 3
V4
V
mRT 0 ln 3
Q
V4
tc 1 0 1
V
Q
mRT ln 2
V1
V
V
But ln 3 ln 2 ,explained as follows :
V4
V1
Q Q1 2 mRT ln

- for 2-3

and

Q0 0 .

T2V2k 1 T3V3k 1
T2V2k 1 T0V3k 1

- for 4-1

T1V1k 1 T4V4k 1

TV1k 1 T0V4k 1
V
V
2 3
V1 V4

When the ratios of volumes are equal, also are their logarithms ratios so they can be
simplified. The expression of the efficiency is:
tc 1

T0
T

Postulate: The efficiency of Carnot cycle does not depend on the natureof the agent, it
depends only on the temperatures of heat sources.
It was established that tc

Q
Lc
T
1 0 1 0 for Carnot cycle.
Q
Q
T

From two expressions of efficiency tc


source and

Q0 T0

Q
T

, Q0 0 - the released heat to cold

Q Q0

0 This function is Carnot function.


T T0

No heat engine works on Carnot cycle.The thermodynamic efficiency t of the


Carnot cycle has maximum values if it is reported at the same temperatures T and T0.

It is considered a Carnot cycle undergone in reverse sense ( anticlock wise or


trigonometric)
1
p
Q
2

Lc
4
Q0

Fig.19. Representation of Carnot cycle (work consuming )inp-V coordinates


Lc 0 - work consuming

- 1-4 adiabatic expansion


- 4-3 isothermal expansion(the agent receives heat Q0 Q43 0)
- 3-2 adiabatic compression
- 2-1isothermal compression (the agent releases Q Q21 0 )
In an inversed Carnot cycle the agent receives Q0at T0 and releases Q at T.This cycle
is characteristic to refrigeration installations.
Q 0, Q0 0, Lc 0 Lc Q Q0 sau Q Q0 Lc

It is called coefficient of performance f

Q0
. It is not of interest that heat is
Lc

released to environment.The value of the coefficient of performance can be higher


than 1.

Course 7.
Chapter 4. Second law of thermodynamics (continued)
4.5.Clausius integral . Entropy
It is considereda reversible thermodynamic cycle 1ab2cd1, which is intersected by
infinite number of adiabates in cycle area.
Q
p
a

b
2

1
d

Q0

Fig.20. Reversible cycle as a sum of elementary Carnot cycles


It will result an infinite number of elementary cycles as abcd. Considering an
elementary cycle, reversible,abcd:
ab isotherme at T constant
bc adiabate
cd isotherme at T0 constant
da adiabate
It is noted Q, the heat quantity received by the agent in elementary isothermal
transformation ab at Tand analogue, Q0, the heat quantity released by the agent in
elementary isothermal transformation cd at T0.
For elementary Carnot cycle, it is expressed the Carnot function.
Q

Q0
T0

Q
T

0 ,then it is integrated , in which Q0 0 .

Q0

0 for
T0
1

1 A2 B

Q
T

all the cycles having the form of abcd and


2

Q
T

Q
Q

0
T 2B T
1A

as the transformation is reversible it

means that in can be performed,directly and reversely,through the same intermediate


states.
1

As

2B

Q
T


1B

Q
T

it results that

1A

Q
T

1B

Q
T

meaning that the integral of the ratio heat-

temperature does not depend on the path, having the same value for path A or B.

For the integral to be independent on the path it is needed as the ratio


diferential.
Clausius noted

Q
to be a total
T

Q
dS - being the mathematical expression of second law,in which
T

S quantity was called entropy.


Entropy S is a state quantity which can be written as S ms in which
specific entropy.
For a reversible cycle, variation of entropy is 0 and dS
2

J
s
is
Kkg

Q
.
T

Q
Q
dS
S 2 S1
,
T
T
1
1
1

Q elementary heat exchange between agent and surroundings at T.


For a reversible, adiabatic transformation

dS

Q
T

Q 0

dS = 0and S = constant,or S 2 S1 .
The reversible, adiabatic transformation is called isentropic because entropy is
constant S ct
Observation: In all transformations above,

Q
is Clausius integral.
T

Ratio Q/T is called reduced heat.


In a reversible Carnot cycle,thealgaebrical sum of reduced heats is zero or Carnot
function is zero.
4.6.Entropy variation of ideal gas
The variation of entropy S is established for any process using general formulas, for
the case of ideal gas.
According to second law dS
dU Q pdV
dI Q Vdp

Q
T

dU pdV

dS
T
fundamental thermodynamics equations

dI

Vdp
dS

Some particular relations for ideal gas are replaced in fundamental equations.
dU mc v dT

dI mc p dT

It will result :

pV mRT

dS

dS

mcv dT mRdV

T
V
mc p dT
T

p mR

V
T

mRdp
p

Integrating the relations


T2
V J
mR ln 2
T1
V1 K
T
p J
ln 2 mR ln 2
T1
p1 K

S 2 S1 mc vm ln
S 2 S1 mc pm

Replacing

temperature

from

S 2 S1 mc vm ln

p2
V
mc pm ln 2
p1
V1

dS

and

integrating,

it

results:

4.7.T-S diagram . Graphical representation of processes in T-S coordinates


The thermodynamic processes may be represented in temperature T-entropy S
coordinates.
T
[K]
2

a
dT

1
T

d
1

c dS

S [J/K]

Fig.21.Representation of a transformation in T-S coordinates


In T-S representation the elementary area area abcd Tds is equal to elementary heat:
Q Tds
2

Q1 2 Q TdS area abcd Q1 2 area122'1'

For any simple transformation of ideal gas for which there were made representation
in p-V coordinates, it must be ploted graphics in T-S coordinates as it follows:
Isochoric transformation V = constant
dS

Q mcv dT

T
T

S 2 S1 mcv ln

T2
T1

In isochoric transformation, entropy varies logharitmically with temperature.


2
T
[K]
N
1

v
A

S [J/K]

Fig.21.Isochoric process in T-S coordinates


1 T
dT
tg v

dS v ct m cv
NB
AB
mc v T (T-temperature scale)
tgv

The segment NB is proportional to cv.In T S diagram,the representation of isochore


is an exponential curve with positive slope.
Isobaric transformationp = constant
dS

T J
Q mc p dT

S 2 S1 mc p ln 2
T
T
T1 K

In isobaric transformation entropy varies logarithmically with temperature.


1 T
dT
tg p

0
dS p ct m c p
AB T mc p (T-temperature scale )
2

T
[K]

N
1

p
A

Fig.22.Isobaric process in T-S coordinates

S[J/K]

Observation: Comparing the formulas showing the slopes of V = constant and p =


constantprocesses, it can be written:
tg v

1 T
1 T
and tg p
m cv
m cp

If are plotted two curves of V = constant and p = constant in the same T- S diagram
the curves intersecting in point N will be distincted as follows the exponential with
higher slope is the isochore and the exponential with smaller slope is the isobar.
T
[K]
V=constant

p=constant
N

p
A

S [J/K]

Fig.23.Comparison between isochoric and isobaric curves in T-S


cp

tg v tg p as cv c p
k k 1
cv

Isothermal transformation(T = constant)


dS

Q
T

Q
Q 1
J
S 2 S1

Q 12
T
T 1
T K
1

Q12 L1 2 p1V1 ln

V2
p
V
p
p1V1 ln 1 mRT ln 2 mRT ln 1
V1
p2
V1
p2

It can be written :
S 2 S1

for T = constant

Q1 2
V
p
mR ln 2 mR ln 1
T
V1
p2

Expansion
Destindere
T

Compression

S2

S1

- Fig.24.Isothermal process in T-S coordinates


- If the process performs from point 1 to point 2 meaning that the difference of
entropy is positive, it means that the heat exchange is positive, the system performs
work and expands. S 2 S1 0 Q12 0 receiving heat.
Adiabatic transformation
Inadiabatic transformation the heat exchange and variation of entropy are zero. Q 0
Q1 2 0

dS 0

S cons tan t

J
S1 S 2
K

- The adiabatic transformation which is also reversible is called isentropic (of constant
entropy).
T

Expansion
eree

Compression
marere

- Fig.25.Isentropic process in T-S coordinates


Polytropic transformation
Q
nk

dS
Q mcn dT m
cv dT

T
n 1

S 2 S1 mcn mediu ln T2 m n k cv med ln T2

T1
n 1
T1

2
Expansion
M
1

p
S

Fig.26.Polytropic process in T-S coordinates


The graphic

of the transformation is exponential with negative slope

1 T
1 n 1 T
dT
tg p


dS pol m cn m n k cv

- for the tranformation having 1 n k


tg p 0
when p belongs to the second trigonometric quadrant, being obtuse.
Observations: 1) In T-S diagram a reversible Carnot cycle is represented as a
rectangle.
Q
1

Q0
T0

Fig.27. Carnot cycle in T-S coordinates


1-2 isothermal expansion it receives heat
2-3 adiabatic expansion
3-4 isothermal compression it releases heat
4-1 adiabatic compression
Q Q12 A12BA Q 0
Q0 Q34

Q Q0 Lciclu
A34 AB Q0 0

2)In T-S coordinates for ideal gas transformations the isochores ( isochoric curves)
are parralel among them,the isobars also, the polytropic curves with the same n are
parralel too.
4.8. Clausius integral and entropy variation in irreversible processes
There are considered two Carnot cycles working between two sourses of heat of
temperatures Tand T0.

The first cycle is reversible and the second is irreversible.


Assuming that : Qrev Qirev
Hot source , T

Qrev

Qirev
Heat
engine II

Heat
engine I

Lcrev

Lcirev

Q0irev

Q0rev
Cold source, T0

Fig.28. Reversible and irreversible cycles with the same sources


Taking into account the characteristics of irreversible processes it results that
Lc irev Lc rev for the same amount of heat Q taken from the hot source.
Lcrev Lc irev so Q0 rev Q0 irev
For reversible Carnot cycle
t
rev

t
irev

Lc rev

Qrev
Lc i rev
Qirev

Q0 rev
Qrev
Q0irev
Qirev

T0
T
Q0 irev
Q0irev T0
Q
irev
0
Qirev T
T
T0

resulting

-expression of Carnot

function for irreversible Carnot cycle.


It is considered an irreversible cycle 1A2B1; the cycle intersects in p V plane with
an infinite number of adiabates.
Q
p
a

b
2

1
d

Q0
V

Fig.29.Decomposing of an irreversible cyle into an infinite number of Carnot cycles


There are formed an infinite number of elementary irreversible Carnot cycles having
the form abcd.

a-b elementary isothermal transformation at constant T


b-c adiabatic transformation
c-d elementary isothermal transformation at constant T0
d-a adiabatic transformation .
The Carnot function for elementary irreversible Carnot cycle abcd is :
Q
T

Q0
T0

Integrating all Carnot function for all elementary irreversible Carnot cycle having the
form abcd,
Q Q0
Q
Q
T T0 0 T 0 ,1A2 B1 T 0

Clausius integral for an irreversible cycle 1A2B1 is negative.


It is considered the cycle 1A2B1 irreversible
1
p
A

B
2
V

Fig.30. Cycle half reversible half irreversible


Assuming that the cycle is made of 1A2 irreversible and 2B1 reversible.

Q
0
T
1A2 B

Q
0
T

Q
Q


0
T
T

rev
irev
1A
2B

Q
In which for reversible transformation
1

T rev

2B

Q
1B T rev 1B dS or
2

Q
1B T rev S 2 S1
2

T rev
1B
2

Q
Q
resulting ( S 2 S1 )0 or S 2 S1
T
T
1 A
1 A
2

The formula expresses the variation of entropy in an ordinary irreversible process.


Differentiating results leads to

dS

Q
irev mathematical formulation of the second
T

law of thermodynamics for irreversible processes.


4.9.Examples of thermodynamic processes,typically irreversible
a)
Heat exchange between two bodies with finite temperature difference.
It is considered an isolated system made of two bodies of different temperatures.

T1

I
Q

T2
II

Fig.31.Adiabatic system
If the first body has a higher temperature than the second one it releases heat towards
the second Q 1-2 T1 T2 Q12
In the system dS0 as th heat exchange at finite difference is an irreversible process.
For body I:the analysis of irreversible process is done replacing real proces with an
equivalent isothermal, reversible process.
S I

Q
Q0
T1

Analog S II

- the body releases Q


Q
Q 0
T2

- the body receives Q

For all the system, adiabatic and irreversible


S S I S II

Q Q
S 0 as T1>T2
T1 T2

b).Gas laminar flow


Definition: A laminar flow is a fluid flow through an orifice with a smaller section
than upstream which is produced by expanding without performing work to
surroundings.
1

w1

w2
p1,T1,i1

p2 ,T2,i2

Fig.32. Laminar flow of gas when passing through a diafragm


The minimum section is downstream orifice. Experimentally were noticed energy
loss (friction and vortices) which turn into heat which is absorbed by fluid, resulting
p 2 p1 .

In order to find out the thermodynamic properties of laminar flow it is written the
first law for closed systems as energy balance.
i2 i1

w22 w12
g h2 h1 q12 lt
2

J

kg

In laminar flow w2 w1 h2 h1 q1 2 negligible .


Gas has the exterior temperature and it is imposed the condition not to perform shaft
work , lt 0 . The condition is obeyed if w2 w1 h2 h1 q1 2 negligible, wich lead to
equality of the enthalpies of the two sections The laminary flow is an isenthalpic
process, resulting i2 i1 .
The analysis of entropy variation: considering that gas has temperature equal to
environmental temperature T0 T the laminar flow can be studied as a adiabatic
irreversible process.
Due to frictions heat is realeased and stored in gas and entropy increases.The
equivalent process do not consider temperature variation the process being replaced
by a reversible isothermal process in which the pressure decreases.
V2
p J
mR ln 1
V1
p2 K
V
p
s 2 s1 R ln 2 R ln 1 - for1 kilo of agent
V1
p2
S 2 S1 mR ln

Questions
1.
2.
3.
4.
5.
6.
7.

What is a thermodynamic cycle?


What is the expression of work in a thermodynamic cycle ?
How are classified the thermodynamic cycles?
Which is the formula for thermodynamic efficiency ?
Enounce the second law of thermodynamics in several versions.
What is Carnotcycle ?Which is its thermodynamic efficiency ?
What is inversed Carnot cycle ?What is coefficent of performance
refrigerating installations?
8. How is defined entropy and which is the connection to second law
thermodynamics?
9. Which is the entropy variation in isobaric transformation and how
represented in T-S coordinates ?
10.Which is the entropy variation in isochoric transformation and how
represented in T-S coordinates ?
11.Which is the entropy variation in isothermal transformation and how
represented in T-S coordinates ?
12.Which is the entropy variation in adiabatic transformation and how
represented in T-S coordinates ?
13.Which is the entropy variation in polytropic transformation and how
represented in T-S coordinates ?
14.What is the influence of irreversibility of processes upon entropy?

of
of
is
is
is
is
is

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