Lecture 2

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FIRST AND SECOND LAWS OF

THERMODYNAMICS

THERMODYNAMICS 1
Content

 Enthalpy and the caloric equation of state


 Wording and equation of the first law of
thermodynamics
 The first law of thermodynamics for the working
medium flow

THERMODYNAMICS 2
Enthalpy

 total energy of an expanded system, including working


medium and the environment
H = U + p·V, J
 specific enthalpy
h = u + p·v, J/kg

THERMODYNAMICS
3
Caloric equation of the system state

for equilibrium state:

h = f (p, T),

where h – specific enthalpy

THERMODYNAMICS 4
Wording of the first law of
thermodynamics

 Perpetual motion machine of the first kind is


impossible.

THERMODYNAMICS 5
First law of thermodynamics

The first law of thermodynamics is the quantitative


expression of the law of conservation and
transformation of energy for the goals of
thermodynamics.
 The notion of energy is inseparably linked with the
matter motion: energy is a physical measure of the
matter motion, and the law of conservation and
transformation of energy expresses the fact of
indestructibility of the material world motion.
 Based on the law of conservation and transformation of
energy can be determined the precise quantitative
relationships between different forms of energy.
THERMODYNAMICS
6
Wording of the first law of
thermodynamics
 Energy of an isolated system is a constant value
E1 = E2 = const

 heat Q delivered to the thermodynamic system is used to


change the system energy (E2 - E1) and do the work L:
Q = E2 – E1 + L, J
q = e2 – e1 + l, J/kg

where (e2 – e1) – specific energy change, J/kg

THERMODYNAMICS 7
Wording of the first law of
thermodynamics

 Perpetual motion machine of the first kind is impossible.


 Previously, it was found that total energy of the fixed
thermodynamic system equals its internal energy U.
 Based on this, in expression Q = E2 – E1 + L we replace energy
change (E2 – E1) with internal energy change (U2 – U1), and work
L with expansion (compression) work Lv.

THERMODYNAMICS 8
Equation of the first law of thermodynamics

 Based on this, analytical expression of the first law of


thermodynamics for m kg is written as:
Q = U2 – U1 + L ,
 i.e., heat Q delivered to the system is used to change
the internal energy (U2 – U1) and do the expansion
(compression) work. For 1 kg of substance the first
law of thermodynamics can be written as:

q = u2 – u1 + l

In the differential form: dq = du + pdv

ТЕРМОДИНАМИКА 9
SECOND LAW OF THERMODYNAMICS
Content

 Wording of the second law of thermodynamics


 Entropy
 Thermodynamic identity

THERMODYNAMICS 11
Wording of the second law of
thermodynamics

“Heat cannot by itself pass “Not all of the heat received from
from a colder to a hotter heat source can be converted
body, i.e., without into work, but only a certain
compensation” part of it. Another part of it
Clausius (1850) must inevitably go into the
heat sink”.
Thomson (1851)

“Perpetual motion machine of


the second kind is
impossible”
Ostwald (1892)

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Wording of the second law of
thermodynamics

1. In an engine running on a cycle it is not possible to


convert all the quantity of heat, received from the heat
source, into work.

2. Heat flow is always directed toward the lower


temperature.

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Statistical formulation of the second law of
thermodynamics

 A closed system of many particles is spontaneously


converted from a more ordered into a less ordered
state (or from a less probable to a more probable).

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 The second law of thermodynamics is a
consequence of the irreversibility of thermal
processes.

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Entropy

ds = dq/T, J/(kgK)

Clausius (1850)

ds is a total differential

s is a function of the system state and is unambiguously


determined by any two thermodynamic parameters:
s = s1(p, v)
s = s2(p, T)
s = s3(v, T)
s = s4(p, h)
etc.
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Entropy

ds = dq/T, J/(kgK)

Clausius (1850)
ds is a total differential

s is a function of the system state and is unambiguously


determined by any two thermal or caloric parameters:
s = s1(p, v)
s = s2(p, T)
s = s3(v, T)
s = s4(p, h)
etc.
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Entropy

Entropy S for mass m of gas equals:

S=ms, J/K

As zero entropy for gas is taken on a value s0=0 at


temperature Т=0 оС.

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Caloric parameters of state

Caloric parameters u, h, s unambiguously describe any


state of a thermodynamic system.

Caloric u, h, s and thermal p, v, T parameters possess


unambiguous correspondence.

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Thermodynamic identity

or basic equation of thermodynamics

Tds = du + pdv

is obtained from dq = du + pdv and dq =Tds


.

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Ts-diagram

2
q = sq. 1–2–s2–s1 =  T(s)ds.
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1
THERMODYNAMICS

IDEAL GAS PROCESSES


Content

 Thermodynamic processes research method


 Ideal gas
 Polytropic process
 Analysis of the basic ideal gas processes

THERMODYNAMICS 23
THERMODYNAMIC PROCESSES
RESEARCH METHOD
The main goal of the study of thermodynamic processes
is to find:
 the finite state parameters, achieved by the process;

 work done;

 heat, transferred during the process.

Thermodynamic studies are based on the first and


second laws of thermodynamics, allowing to obtain the
calculated ratios for specific processes.

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THERMODYNAMIC PROCESSES
RESEARCH METHOD

To calculate the reversible processes required:


 thermal equation of state f (p, v, T) = 0

 state functions u, h, s, etc.

or
 Dependences of heat capacity cp or cv on parameters
state

When calculating the irreversible processes, finite


parameters can be determined by replacing irreversible
transition from state 0 to state 1 with reversible one.

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Notion of ideal gas

Notion of ideal gas is a scientific abstraction,


which is a limiting case of real gases diluted:

 no interaction forces between molecules;


 molecular size is much smaller than intermolecular
distances.

THERMODYNAMICS 26
Ideal gas equation

 Clapeyron (1834)
 pv=RT
where R – gas constant, J/(kg·K)
 for mass m
 pV=mRT
where V - volume, occupied by gas, m3
 for one kmol
 pV  R T
where Vμ – molar volume, m3/kmol
Rμ = 8314,4 – molar gas constant, J/(kmol·K)
THERMODYNAMICS 27
Molar gas constant

p0V 0 1, 0133 105  22, 4


R    8314 J /(kmol  K )
T0 273,15

Knowing Rμ, can be found a gas constant R for any gas,


using the value of its molecular mass μ:

R
R
The molar mass μ kg/kmol for some gases have the following values:
nitrogen – 28, ammonia – 17, argon – 40, hydrogen – 2, air – 29, oxygen
– 32, carbon oxide – 28, carbon dioxide – 44.
THERMODYNAMICS 28
Heat capacity, enthalpy and entropy
of ideal gases

 The dependence of heat capacity of ideal gas on


the parameters can be determined based on the
general ratios. In addition, for ideal gas:

du dh
0 and 0
dv T dp T

 whereby, heat capacities cp and cv of ideal gas


depend on temperature only
cp ,c v f(T)
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Mayer equation

cp - c v R

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Polytropic process
The process, characterized by a constant value of heat
capacity cn, is called polytropic.

General thermodynamic equation for any processes can be


obtained from the equations:
 First law of thermodynamics dq = cvdT + pdv
 Clapeyron pv = RT
 Mayer cv = cp - R
Solving these equations, we obtain:
cp cn dv dp
n n 0
cv cn v p
where n – polytropic index
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Polytropic process equation

 After integration we obtain the equation of polytropic


process
pv n const
 Using the ideal gas equation pv = RT, we obtain:
1-n
Tv n-1 const Tp n
const
 The expression for heat capacity of a polytropic
process
n k
cn cv cv R(n 1)
n 1
cp
 where k – Poisson ratio
cv 32
Change of internal energy and enthalpy in the
polytropic processes of ideal gas

u u2 u1 cv (T2 T1 )

h h2 h1 cp (T2 T1 )

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Polytropic process heat

q cn (T2 T1 )

n k
q cv (T2 T1 )
n 1

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Specific work of polytropic process expansion

R
pdv = (T1 T2 )
n 1
Factor out T1 and replace RT1 with p1v1
p1v1 T2
(1 )
n 1 T1
or .

p1v1 p2 n 1
1
n 1 p1 n

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Specific technical work

Work of 1 kg of gas in a continuous flow is linked with


expansion work by the following dependence
tech p1v1 p2 v2
For ideal gas pv = RT, then

tech R(T2 T1 )
Substituting the value l, we write
n
tech R(T1 T2 )
n 1
tech n 36
Special cases of polytropic process

 n=0 – isobaric process


 n=1 – isothermal process
 n=– isochoric process
 n=k – adiabatic process

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Analysis of the basic ideal gas processes

Processes in pv-diagram, Ts-diagram

 isobaric process
 isothermal process
 isochoric process
 adiabatic process

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Analysis of the basic ideal gas processes

Parameters ratio

 isobaric process
 isothermal process
 isochoric process
 adiabatic process

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Analysis of the basic ideal gas processes

The change in internal energy, enthalpy, and entropy

 isobaric process
 isothermal process
 isochoric process
 adiabatic process

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Analysis of the basic ideal gas processes

Heat and work

 isobaric process
 isothermal process
 isochoric process
 adiabatic process

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ISOCHORIC PROCESS
 In the isochoric process, specific volume v remains
constant, but pressure and temperature of the working
medium change. Isochores in Ts-coordinates
are logarithmic curves. The
smaller the value of specific
volume v, the more to the left
will pass an isochore, i.e., the
smaller the entropy value will
be at a predetermined
temperature T.
As for ideal gas h = cpT, then
hs-diagram will bear a
complete similarity to Ts-
diagram. 42
v1>v2
ISOCHORIC PROCESS
 Using the equation of ideal gas state pv = RT, we obtain
the process equation
p2 T2
=
p1 T1
 Polytropic index of isochoric process:
cp cv
n =
cv cv
 Process specific heat:
qv u2 u1 + pdv u2 u1 c v (T2 T1 )

 Specific work of volume change:


d v pdv 0 v 0 43
ISOBARIC PROCESS
In the isobaric process, pressure p remains constant,
but volume and temperature of the working medium
change.
Isobars, like isochores, are
logarithmic curves.
As cp > cv, then Δsp > Δsv, so
isobars become flatter than
isochores.
Higher pressure isobars are
located to the left of the lower
pressure isobars.

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р2>р1
ISOBARIC PROCESS
 Using the equation of ideal gas state pv = RT, we obtain
the process equation
v 2 T2
=
v1 T1
 Polytropic index of isobaric process:
n 0
 Process specific heat:
qp h2 h1 vdp h2 h1 cp (T2 T1 )

 Specific work of volume change:

d p pdv p p(v 2 v1 ) R(T2 T1 )


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ISOTHERMAL PROCESS
In the isothermal process, temperature remains
constant, but pressure and specific volume of the
working medium change.

Isotherm in pv-coordinates
is an equilateral hyperbola.
In pv-diagram isotherm is an
equilateral hyperbole, but in
Ts-diagram – a horizontal
line.

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ISOTHERMAL PROCESS
 Using the equation of ideal gas state pv = RT, we obtain
the process equation
p2 v 2
=
p1 v1
 Process polytropic index:
n 1
 Process hat capacity ct
 Change in internal energy and enthalpy equals:
ut h 0
 In the isothermal process of ideal gas its internal energy
and enthalpy remain constant.

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ISOTHERMAL PROCESS
 To calculate the amount of heat delivered, use the first law
of thermodynamics
dq = du + pdv
 As du = 0 q = = pdv

 Replace p with RT/v and obtain after integration


v2 p1
q = = RTln = RTln
v1 p2
 For the isothermal process the expansion work equals the
technical work.
This follows because the isotherm in pv-coordinates is an
equilateral hyperbola.
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ADIABATIC PROCESS

 In the adiabatic process, heat is not delivered to or


rejected from the working medium.
 For the reversible adiabatic processes, entropy
remains a constant value s = const, since dq = Tds
= 0.
 At the adiabatic expansion or compression,
temperature, pressure, and volume of gas change.
 Heat capacity of the adiabatic process cs = 0, since
dq = cdT = 0

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ADIABATIC PROCESS
 Polytropic index:
cp
n= =k
cv
where k – adiabatic index or Poisson ratio
 All ratios given are obtained by replacing the polytropic
index n with the adiabatic index k

 Equation of adiabatic process: pv k const


1-k

 whereof Tv k-1 const Tp k


const

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ADIABATIC PROCESS
 Specific work of expansion (compression):
R p1v1 p2 k -1
(T1 T2 ) 1
k -1 k 1 p1 k
 Specific technical work:
k
tech R(T1 T2 )
k 1
 or tech k
 All ratios given hold only for monatomic ideal gases, since
their heat capacities cv and cp don’t depend on temperature.
 For di- and polyatomic gases cv, cp = f(T) and,
consequently, the adiabatic index k = f(T) also depends on
temperature.
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Behavior of the adiabatic process in pv- and Ts-
diagrams

Show that in pv-diagram adiabatic is of the form of a


hyperbole, which is steeper than an isotherm.
After differentiating the equations of isothermal pv = const
and adiabatic processes pvk= const, we obtain
p p p p
k
v t v v s v
i.e., an adiabatic is k times steeper than an isotherm.
In Ts-diagram, a reversible adiabatic is shown as a vertical
line.

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Behavior of the adiabatic process in pv- and Ts-
diagrams

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MIXTURES OF IDEAL GASES
Content

 Gas mixture design


 Gas mixture laws

ТЕРМОДИНАМИКА 55
BASIC NOTIONS AND DEFINITIONS

 Thermodynamic processes don’t usually involve


pure gases but gas mixtures
 air - gas mixture mainly consisting of nitrogen and oxygen;
 products of combustion in furnaces of steam boilers and
internal combustion engines, etc.
 Each gas mixture is subject to the same
thermodynamic laws as homogeneous gases
 For gas mixtures go through all equations obtained
for pure gases

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Mixture of ideal gases

 A mixture consists of several ideal gases, which don’t


react with one another;
 Some gases, included in the mixture, are called
mixture components;
 The main goal of calculating gas mixtures is to
determine the thermal parameters (pressure and
volume) and state functions (internal energy, enthalpy,
entropy, etc.)

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Gas mixture design

 To characterize gas mixture design, the notion of


concentration is introduced.
 Depending on the measurement units of components,
the following kinds of concentration are given:
 mass concentration g;

 molar concentration z;

 volume concentration r.

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MASS CONCENTRATION
 Let m denote the mixture mass, and m1, m2, m3, etc.,
denote the mass of each component (gas) included in
the mixture, then total mixture mass equals
m = m1 + m2 + m3 + …
 Hence, mass concentrations (fractions) of separate
components g1, g2, g3, etc., equal

m1 m2 mi
g1 g2 gi
 or m m m
g1 g2 g3 ... 1
 i.e., the sum of all mass fractions equals one.
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VOLUME CONCENTRATION

 Let v denote the mixture volume, having pressure p and


temperature T, and V1, V2, V3, etc., denote the volume of a
separate component (gas) at pressure and temperature of
the mixture, then the total mixture volume equals
V = V1 + V2 + V3 + …,
where V1, V2, V3,..- partial volumes of mixture components
 Additivity rule for the mixture volume of ideal gases v is
due to the fact that each mixture component behaves
“independently” with respect to the other gases, since
there is no interaction between molecules (mass points) of
ideal gas.
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VOLUME CONCENTRATION

 Given this issue, volume concentrations (fractions) of the


components r1, r2, r3, … equal
V1 V2 V3
r1 r2 r3
or V V V
r1 + r2 + r3 + … = 1,
 i.e., the sum of all volume fractions equals one.

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Relationship between the mass and
volume concentrations

mi Vi i i
gi ri
m V

Vi
ri 
V

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Gas mixture laws

 Dalton law
 Clapeyron equation
 Avogadro law

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Partial volumes and partial pressures of
gas mixture
 Assume that in the cylinder of constant volume at the
pressure p and temperature T is stored gas mixture,
e.g., air, consisting of nitrogen and oxygen (neglecting
other components).
 In case of removing nitrogen at a constant
temperature T from the cylinder, the pressure of
oxygen decreases to a value called the partial oxygen
pressure in the mixture.
 Partial pressure рi – pressure that a gas mixture
component has if itself, at the same temperature, fills
the whole mixture volume V.

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Dalton law

Total mixture pressure p equals the sum of partial


pressures of separate gases:

n
p  p1  p2  ...  pn   pi .
i 1

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THERMODYNAMIC STATE FUNCTIONS

 The fact that ideal gas possesses no interaction


forces between molecules allows calculating
thermodynamic properties and state functions
based on the additivity rule, which greatly simplifies
the calculations.
Consequently:
 mixture internal energy u = Σgjuj;

 mixture enthalpy h = Σgjhj

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HEAT CAPACITY OF IDEAL GASES MIXTURE

 isochoric heat capacity of mixture cv = Σgjcvj


 isobaric heat capacity of mixture cp = Σgjcpj

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Clapeyron equation

рiV=miRiT

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