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Definitions of Thermodynamics:
can be defined as the science of ENERGY
ENERGY :
might be difficult to define precisely, but
we can view it as AN ABILITY TO
CAUSE CHANGES
PE = 7 units
KE = 3 units
Hot cold
decreasing quality
Space
Surroundings
The mass or region outside the system.
Boundary
The real or imaginary surface that separates
the system from its surroundings.
Covenant University, Dept. of Chemical
11/3/2017 29
Engineering, Thermodynamics (GEC 221)
NOTE
The boundary is the contact surface shared by
both the system and the surroundings.
Mathematically speaking, the boundary has zero
thickness, and thus it can neither contain any
mass nor occupy any volume in space.
SURROUNDINGS
BOUNDARY
E, M
X E, M
E
Closed
X M
Molar volume
V = Vt/n or Vt = nV 2
Q=0
ADIABATIC
AA
SYSTEM
Insulation
T = E/Cp 8a
Energy
Energy is difficult to define. Many define it as
ability to do work. It is beyond this. Suffice to
say that energy exists as heat, mechanical
(potential, volume, kinetic), chemical,
magnetic, nuclear, and electrical forms.
50oC 23oC
33oC 33oC
40oC 30oC
35oC 33oC 33oC
33oC
44oC 20oC
Quasi-equilibrium expansion
and compression of a gas
Frictionless pendulum
B
SYSTEM
A C
A+CB=0 10
By convention, input to system is +ve
and output is ve.
Covenant University, Dept. of Chemical
11/3/2017 77
Engineering, Thermodynamics (GEC 221)
Technical Definition of Thermodynamics
On the basis of the our discussions so far,
thermodynamics can be defined as the
science that considers the relationship
between a quantity of energy that causes/
accompanies a change of state from 1 to 2,
and the properties in State 1 and State 2.
(E) = f( P1, P1, P1 P2, P2, P2) 11
Ut = Q + W 14
where Ut = mU or Ut = nU
Equation 14 is for a finite closed system
Covenant University, Dept. of Chemical
11/3/2017 86
Engineering, Thermodynamics (GEC 221)
For differential changes:
dUt = dQ + dW 15
For closed system of n moles, Eq. 14 and Eq. 15
may be written as
(nU) = n U = Q + W 16
d(nU) = ndU = dQ + dW 17
Note that Q and W are extensive properties and
not thermodynamic properties. They depend
on their history. Thermodynamic properties
are unique, not ambiguous i.e. not dependent
on path. dW and not W
Covenant University, Dept. of Chemical
11/3/2017 87
Engineering, Thermodynamics (GEC 221)
What makes Eq. 17 a thermodynamic
equation is that the LHS of the equation is a
thermodynamic property - the beginning and
end conditions are specified irrespective of
the paths.
The fact that the factors on the RHS are not
thermodynamic properties implies that the
specific conditions have to be specified for
thermodynamic states to be met.
= P2 P1 = P and
= V2 V1 = V
U = (constant V) 29
and H = ( constant P) 33
= M , q = uA 35
Covenant University, Dept. of Chemical
11/3/2017 110
Engineering, Thermodynamics (GEC 221)
= uA 36
= uA 37
A = cross sectional area, = density.
Although velocity is a vector quantity, its scalar
magnitude, u is used as the average speed of a
stream in the direction normal to A.
Note that all the flow rates represent measure
of quantity per unit time, however, u does not
suggest the magnitude of flow.
1 CONTROL VOLUME
dmcv/dt
CONTROL
2
SURFACE
38
is the accumulation
(if depletion, its negative) of mass.
=
When is written in terms of Eqs. 36, 37 and
38 becomes
= 0 40
= Constant = 41 =
E1 E2
43
Or as 44
If no work, in form of pumping say, is done on
the system, a combination of Equations 43
and 44 yields;
m -m
= Q - (PV) m 45
Covenant University, Dept. of Chemical
11/3/2017 120
Engineering, Thermodynamics (GEC 221)
H = U + PV, Eq. 45 becomes
46
This equation is applicable to a situation of
steady state flow (the fluid properties at an
inlet or exit remain constant, i.e. do not
change with time), with internal friction in the
fluid but no shaft work done.
Eq. 46 may have been obtained from over
simplification of the conditions applied in
Figure 2
Covenant University, Dept. of Chemical
11/3/2017 121
Engineering, Thermodynamics (GEC 221)
For more practical purposes, other types of
work such as stirring, etc. may have gone into
the system. With stirring, for example Eq. 46
becomes
48
Where are on unit mass basis.
reduces to
H2 = H1 + Q where
PV = RT 50
The equation is for an ideal gas. This is the
simplest best known equation of state for
substances in the gas phase. The equation
predicts the P-v-T behaviour of a gas quite
accurately within some properly selected
region.
Covenant University, Dept. of Chemical
11/3/2017 137
Engineering, Thermodynamics (GEC 221)
However, industrial processes for which
thermodynamics are intended for applications go
beyond ideal gases to pure and mixture of gases,
liquids and solids.
They also go beyond PVT relations to others from
which properties such as enthalpy, H, entropy, S
etc can be obtained.
Accordingly, equations of state, which Eq. 50
represents, can be developed for virtually all
industrial conditions.
The variations of properties during phase-change
processes are best studied and understood with
the help of property diagrams/relations.
11/3/2017
Covenant University, Dept. of Chemical
138
Engineering, Thermodynamics (GEC 221)
PVT Behaviour of Pure Substances
1.P-T Relation (Figure 4)
Isothermal compressibility
Covenant University, Dept. of Chemical
11/3/2017 146
Engineering, Thermodynamics (GEC 221)
A combination of Eqs. 51, 52 and 53 yields
= 55
59
= 83.1447c K-1
CI = 64
DI = 65
dQ = CVdT + 68
Substituting 68 into 17,
dW = - RT . 69
with
and dW = - R dT + RT . 71
with
work is simply
dW = - P dV and
dQ = dP + P dV . 72
and H = = 0
Similarly write Eqs. 68 and 70,
Covenant University, Dept. of Chemical
11/3/2017 173
Engineering, Thermodynamics (GEC 221)
=
=
Note that Q = -W, a result which also follows
from Eq. 14
Q = -W =
(const. T)
11/3/2017
.. 73
Covenant University, Dept. of Chemical
174
Engineering, Thermodynamics (GEC 221)
Isobaric Process
From previous equations
U = and H =
Note that Q = H
Q = H = (const. P) .. 74
Q = U = Const. V . 75
Covenant University, Dept. of Chemical
11/3/2017 176
Engineering, Thermodynamics (GEC 221)
Adiabatic Process; Constant Heat Capacities
An adiabatic process is one for which there is
no exchange of heat between the system and
the surroundings,
and =
given that .. 77
HEAT
HEAT
Thermal energy
SINK
Heat
Qc
Tc
Figure 10. The principle of heat engines
Covenant University, Dept. of Chemical
11/3/2017 197
Engineering, Thermodynamics (GEC 221)
A heat engine is a system which converts heat QH
drawn from a higher temperature TH, to work, W,
and discharges residual heat Qc, at a lower
temperature Tc.
The principle of the heat engine is illustrated in
Figure 10.
The practice of a heat engine requires that a heat
exchanger brings about heat exchange between a
reservoir at each of hot and cold ends, where the
heat exchange takes place through a fluid called a
working fluids, as presented in Figure 11.
W Pump Turbine W
Condenser
Figure 11. Practice of heat engines Qc
Covenant University, Dept. of Chemical
11/3/2017 200
Engineering, Thermodynamics (GEC 221)
Thermodynamic representation of Heat Engine
P
1 2
Constant Entropy & Enthalpy
Constant Entropy
4 3
Figure 12 H
Covenant University, Dept. of Chemical
11/3/2017 201
Engineering, Thermodynamics (GEC 221)
The term heat engine is often used in broader
sense to include work producing devices that do
not operate in a thermodynamic cycle.
Engines that involve internal combustion such as
gas turbines and car engines fall into this
category. These devises operate in a mechanical
cycle but not in a thermodynamic cycle since the
working fluid (the combustion gases) does not
undergo complete cycle. Instead of being cooled
to the initial temperature, the exhaust gases are
purged and replace by fresh air-and-fuel mixture
at the end of the cycle.
Covenant University, Dept. of Chemical
11/3/2017 202
Engineering, Thermodynamics (GEC 221)
The work producing device that best fit into
the definition of a heat engine is the steam
power plant, which is an external combustion
engine. That is, combustion takes place
outside the engine, and the thermal energy
released during the process is transferred to
the steam as heat.
Schematic of a basic steam power plant is
shown in figure 11.
= =
HEAT W = 55 MJ
ENGINE
Qc = 45 MJ
Tc The atmosphere
The most efficient heat engines reject almost one-half of the
energy they receive as waste heat.
Covenant University, Dept. of Chemical
11/3/2017 211
Engineering, Thermodynamics (GEC 221)
For to be unity, i.e. net work produced be
equal to the heat responsible for the
production of the work, i.e. efficiency 100%,
Qc must be zero!
No engine has ever been built that
approaches this result; heat is always rejected
to the cold reservoir.
This observation from engineering experience
is the basis for statement 1 and 1a of the
second law.
and as a result
1<2 2=3
= 0
or = and
QH
P TH
1 Isothermal Boiling 2
W
4 Isothermal Condensation 3 3I
Tc
QH
11/3/2017
Covenant University, Dept. of Chemical
Engineering, Thermodynamics (GEC 221)
H 226
Solution
[b] The temperature drop of the heat engine is the
temperature difference between the boiler and condenser
2800C 1200C = 1600C
[c] The Rankine thermal efficiency, , of the system,
work done H2 H3
= = where
heat obtained H2 H1
H is enthalpy of water
Figure subscripts indicate points in the engines cycle of
operation
H2 = saturation enthalpy of water vapour at 2800C
S2 = saturation entropy (S) of water vapour at 2800C
Since operation 2 3 is isentropic, S3 = S2.
Covenant University, Dept. of Chemical
11/3/2017 227
Engineering, Thermodynamics (GEC 221)
solution
H4 = the saturation enthalpy of liquid water at 1200C
Since Operation 4 1 is isenthalpic, H4 = H1.
S3I = entropy of saturated vapour at point 3I (1200C).
From Steam tables,
H2 = 2780.4 kJ/kg
S2 = 5.8586 kJ/kg.K
S3 = 5.8586 kJ/kg.K
H4 = 503.7 kJ/kg
H1 = 503.7 kJ/kg
S3I = 7.1293 kJ/kg.K
S4 = 1.5276 kJ/kg.K
H3I = 2706 kJ/kg
Covenant University, Dept. of Chemical
11/3/2017 228
Engineering, Thermodynamics (GEC 221)
Solution
Calculation of H3
If an enthalpy balance is to be carried out along the
equilibrium temperature of 1200C, i.e 4 3 3I, on
the Heat Engine cycle, the vapour or water quality
of the wet vapour at point 3 is not known.
However, the entropies at points 3 and 3I and 4 are
known. Thus, an entropy balance, will give the
quality of the vapour at point 3,
W
4 Isothermal Condensation 3 3I
Tc = 1 C
QH
11/3/2017
Covenant University, Dept. of Chemical
Engineering, Thermodynamics (GEC 221)
H 237