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Thermodynamics
Science of Energies.
Study of science of transfer &
Conversion of Energies from one
form to another and the study of
properties and characteristics of
matter needed for this transference.
Greek words: therme (heat) + dynamis
(power)
Thermodynamics Power developed
from heat
Types Of Thermodynamics
Classical thermodynamics formulate
the macroscopic state
Studies the average behavior of large
groups of Molecules
Defines macroscopic properties such as
temperature and pressure.
Statistical thermodynamics
formulate the microscopic state
Defines the properties of a system
based on the behavior of
molecules/atoms.
Basic Thermodynamic
definitions
A system contains a substance with a large amount of
molecules or atoms, and is formed by a geometrical volume
of macroscopic dimensions subjected to controlled
experimental conditions
A simple system is a single state system with no internal
boundaries, and is not subject to external force fields or
inertial forces
A composite system has at least two simple systems
separated by a barrier restrictive to one form of energy or
matter
The boundary of the volume separates the system from its
surroundings
A system may be taken through a complete cycle of states, in
which its final state is the same as its original state
Open system:
Material and energy content are variable
Systems freely exchange mass and energy with their
surroundings
Other systems
Isolated system:
Cannot exchange energy and matter
Thermally insulated system:
System surrounded by an insulating
boundary
Universe:
A system and its surroundings
Processes
Energy conversion and degradation:
physical and chemical processes A process takes place in
a system!
Adiabatic process:
Any process within an adiabatic system (no heat transfer
through the system boundaries)
Infinitesimal process:
A process that takes place with only an infinitesimal change in
the macroscopic properties of a system
Thermodynamic properties
are derived from the statistical averaging of
the observable microscopic coordinates of
motion
If a thermodynamic property is a state
function
its change is independent of the path
between the initial and final states
depends on only the properties of the initial
and final states of the system
The infinitesimal change of a state function
is an exact differential
Energy
Mechanical work of expansion or compression
proceeds with the observable motion of the coordinates of
the particles of matter
Chemical work proceeds with changes in internal
energy due to changes in the chemical composition (mass
action)
Potential energy is the capacity for mechanical
work
related to the position of a body
Kinetic energy is the capacity for mechanical work
related to the motion of a body
Potential and kinetic energies are external energies
Sensible heat and latent heat are internal energies
State Of Equilibrium
We only Apply Thermodynamics at
equilibrium
Mechanical
Mechanical Equilibrium
Equilibrium
no unbalanced forces
Chemical Equilibrium
no chemical potential differences
Thermal Equilibrium
no temperature differences
Phase Equilibrium
No phase change
Zeroth Law
Object A is in equilibrium with both
the thermometer and object B. Then
the thermometer should also be in
equilibrium with object B.
This means all three objects have the
same temperature
Temperature scales
Substance gas
Property limit(pV)
Reference point
Interpolation
f (t)
Limit (pV)
p
0
Slope R
f(t) = Pv at triple point of water T = 22711.8
273.15 K
273.15K
Absolute Zero
-273.15 C
f (t)= pV=0
0C
100 C
t (C)
Work: P-V
Internal Energy U
No concise thermodynamic definition
Cannot be directly measured
Only absolute values are known
(no reference point)
In thermodynamics, only changes in
internal energy are used
U=U2-U1
First law of
thermodynamics:
Conservation of energy
During a process:
Energy can be transferred and
converted from one form to another,
while the total energy remains
constant
(Energy of the system) + (Energy
of the surroundings) = 0
Finite change in quantity
Constant-V and
Constant-P Process
Energy balance for n moles of a
homogeneous fluid contained in a
closed system:
d(nU) = dQ + dW
Mechanically reversible, closed
system:
dW = -Pd(nV)
Then d(nU) = dQ - Pd(nV)
@ Constant-V
If V = cnst dV = 0
for closed system dn = 0 dW = -Pd(nV) =
0
Then
@ Constant-P
Enthalpy
Is used to calculate cooling and
heating processes (heat exchangers,
evaporators, distillation columns,
pumps, turbines, engines, etc)
appears in energy balances to
calculate Q and W
Solution:
System: 1 kg water @ constant T
Assumption: Mechanically reversible, closed,
constant P system
H = Q = 2256.9 kJ
H = U + (PV)
U = H PV
PV = 101.33 kPa * (1.673-0.00104) m3
=169.4 kJ
U = 2256.9 - 169.4 = 2087.5 kJ
MEASURE
OF DEVIATION FROM IDEAL-GAS
The farther away Z is from unity, the more the
Compressibility factor Z
BEHAVIOR
gas deviates from ideal-gas behavior.
A factor that accounts for
the deviation of real gases
from ideal-gas behavior at
a given temperature and
pressure.
Reduced
temperature
Pseudo-reduced
specific volume
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Principle of Corresponding
States
B/ r 12
A/r 6
Virial EOS
Generally applicable to moderate
deviations from ideal gas behavior,
the virial EOS is given by two
alternate forms:
Pitzer Correlation
Acentric Factor
The compressibility factor for all fluids with
the same value of , when compared at the
same reduced temperature and pressure are
approximately the same, and hence the
deviation from ideal-gas behavior is nearly
the same.
Generalized Compressibility factor
Approach to EOS: Pitzer Correlations
OTHER EQUATIONS OF
STATE
Critical isotherm
of a pure
substance has
an inflection
point at the
critical state.
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