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THERMODYNAMICS Presentation
THERMODYNAMICS Presentation
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
1. Human Existence
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
08/11/2022 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
SYSTEM
BOUNDARY
E, M
X E, M
E
Closed
X M
• Molar volume
V = Vt/n or Vt = nV …2
ADIABATIC
Q=0
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+C–B=0 …10
•By convention, input to system is +ve
and output is –ve.
Covenant University, Dept. of Chemical
08/11/2022 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, P’1, P”1 … P2, P’2, P”2…) …11
∆Ut = Q + W …14
where Ut = mU or Ut = nU
Equation 14 is for a finite closed system
Covenant University, Dept. of Chemical
08/11/2022 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
08/11/2022 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 = ΔPand
= V2 – V1 = ΔV
∆U = (constant V) …29
Equation 24
Covenant University, Dept. of Chemical
08/11/2022 108
Engineering, Thermodynamics (GEC 221)
Q = n∆H = n (constant P) …34
= M , q = uA …35
1 CONTROL VOLUME
dmcv/dt
CONTROL
2
SURFACE
…38
is the accumulation
(if depletion, it’s negative) of mass.
=
When is written in terms of Eqs. 36, 37 and
38 becomes
= 0 …40
…41 =
= Constant =
In terms of volumetric flow rate, equation 41
can be written as:
= = = …42
This form of continuity equation is frequently
used.
Covenant University, Dept. of Chemical
08/11/2022 116
Engineering, Thermodynamics (GEC 221)
THE GENERAL ENERGY BALANCE
The law of conservation is as equally applicable
to energy as it is for mass.
For a fluid in motion as in Figure 2 below:
E1 E2
The…43total energy of a
simple compressible system consists of three
parts for a non-flowing fluid (U, K.E., P.E.) and
four parts for a flowing fluid (flow energy/
flow work : Pv, U, K.E.,P.E). v, is volume/mass
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
08/11/2022 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
+
Furthermore, if changes in potential and
kinetic energies become negligible with
respect to enthalpy changes, we may have,
Nozzles
V and diffusers
Nozzle are
V >> Vshaped
V Diffuser
so that they
1
V << V 2 1
1 2 1
reduces to
H2 = H 1 + 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
08/11/2022 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.
Covenant University, Dept. of Chemical
08/11/2022 138
Engineering, Thermodynamics (GEC 221)
PVT Behaviour of Pure Substances
1.P-T Relation (Figure 4)
Isothermal compressibility
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Covenant University, Dept. of Chemical
146
Engineering, Thermodynamics (GEC 221)
A combination of Eqs. 51, 52 and 53 yields
= …55
…59
• = 83.1447c K-1
CI = …… 64
DI = …… 65
dW = - RT …. 69
with
and dW = - R dT + RT …. 71
with
work is simply
dW = - P dV and
dQ = dP + P dV …. 72
and ΔH = = 0
Similarly write Eqs. 68 and 70,
=
Note that Q = -W, a result which also follows
from Eq. 14
Q = -W =
Note that Q = ΔH
∴ Q = ΔH = (const. P) ….. 74
∴ Q = ΔU = Const. V …. 75
Integrating with
08/11/2022 constant gives
Covenant University, Dept. of Chemical
Engineering, Thermodynamics (GEC 221)
177
=
Similarly Eq. 70 and 72 lead to
=
and =
HEAT
HEAT
Thermal energy
SINK
Heat
Figure 9. Work can always be converted to heat directly and completely, but the reverse
is not true
Covenant University, Dept. of Chemical
08/11/2022 193
Engineering, Thermodynamics (GEC 221)
• The mechanical work done by the shaft as
shown is first converted into internal energy of
the water.
• This energy may then leave the water as heat.
Attempt to reverse this process will fail.
• Transferring heat to the water does not cause
the shaft to rotate.
• From this we conclude that work can be
converted to heat directly and completely, but
converting heat to work requires the use of
some special devises. These devises are called
heat engines
Covenant University, Dept. of Chemical
08/11/2022 194
Engineering, Thermodynamics (GEC 221)
Heat engines differ considerably from one
another, but all can be characterized by the
following:
• They receive heat from a high-temperature
source (solar energy, oil furnace, nuclear
reactor, etc)
• They convert part of this heat to work (usually
in the form of a rotating shaft).
• They reject the remaining waste heat to a low-
temperature sink (the atmosphere, rivers, etc)
• They operate in a cycle.
Covenant University, Dept. of Chemical
08/11/2022 195
Engineering, Thermodynamics (GEC 221)
TH
QH
Qc
Tc
Figure 10. The principle of heat engines
Covenant University, Dept. of Chemical
08/11/2022 196
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.
Covenant University, Dept. of Chemical
08/11/2022 197
Engineering, Thermodynamics (GEC 221)
• Heat engines and other cyclic devices usually
involve a fluid to and from which heat is
transferred while undergoing a cycle. This fluid
is called the working fluid.
W Pump Turbine W
Condenser
1 2
Constant entropy and enthalpy
Constant entropy
4 3
H
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Figure 12
Covenant University, Dept. of Chemical
200
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
08/11/2022 201
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.
η= =
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
08/11/2022 210
Engineering, Thermodynamics (GEC 221)
• For η 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.
1 2 3
Irrev. Rev. Rev.
HE HE HE
η1<η2 η2=η3
Low-temperature reservoir at TC