ADVANCED THERMODYNAMICS AND

COMBUSTION (MENG6102)
By
Dinku Seyoum (PhD)
Mr. Merera
 CHAPTER 5
Entropy
Thermodynamics deals with stability of systems.
o What is state function?

A state function of a thermodynamic system that is dependent on initial and final state. (Mass, Energy –
enthalpy, internal energy, Gibbs free energy, etc., Entropy, Pressure, Temperature, Volume, Chemical
composition and Altitude)

o What is process function?

A process function is a thermodynamic term that is used to name a property whose value depends on the
path taken to reach specific value. Different paths have different values.

when expressing the path function mathematically, multiple integrals and limits are required to integrate
the path function. Eg. (Mechanical work, heat and arc length are process functions )

∆U = q + w ∆U = state function but w and q is process function.

Process function
No Process Type Constant Q W
Quantity
1 Isobaric P 𝑛𝐶𝑃 ∆𝑇 𝑃∆𝑉

2 Isothermal T 𝑉𝑓
𝑛𝑅𝑇𝑙𝑛 𝑉𝑖
3 Isochoric V ∆𝑈

4 Adiabatic 𝑃𝑉 𝛾 0 −∆𝑈

∆𝑈 = 𝑛𝐶𝑣 ∆𝑇
Second Law of Thermodynamics

o Many formulations. Consider the following two.

1. Spontaneous (i.e. without external agent) transfer of heat from cold object to
hot object is impossible.
2. No Perpetual Motion Machine of second type. (device that realizes full
conversion of heat into useful work, without any “side effect”, in contrast with
real engines.)
In 1st Law of thermodynamics (for infinitesimal process) δQ = dU+ δW
δQ = not function of state, depends on process
Entropy
o If T=constant : ∆Q=T∆S
There exist one more function of state = Entropy
o ∆S = 0 for adiabatic process
∆S ≠ 0 for non-adiabatic
o In thermodynamics there are
4 variable (P,V,T, S)

REVERSIBLE IRREVERSIBLE
Series of quasi-static (equilibrium) steps Series of complex, non- equilibrium steps
No dissipation (e.g. no friction) Dissipation may be present
Any process that can be represented as a Any process that is sudden, spontaneous,
path on a PV diagram; e.g (Isochoric, uncontrolled, or involves dissipation
Isobaric, Isothermal and Adiabatic) Eg (Free expansion, Explosion, Heat
transfer between a hot, and a cold object,
Volume changes of gas with a piston that
has friction)
Entropy change for reversible process

Entropy change for adiabatic process? General process: (Ti, Vi, pi) --> (Tf, Vf, pf)

𝑇𝑓 𝑉𝑓
∆𝑆 = 𝑛 𝐶𝑣 𝑙𝑛 𝑇𝑖 + 𝑅𝑙𝑛 𝑉𝑖
o Intuitively: Entropy = Measure of Disorder
With time, entropy of isolated system: increases in irreversible process, remains
the same in reversible process:
If you reach “thermal equilibrium” with untidy roommate, that would correspond
to maximum possible disorder.
 How can we extract heat? Heat Engines
Heat engine takes some substance (e.g. gas) through cyclic
process during which:
o Heat QH absorbed from hot reservoir
o Work W+ done by engine
o Heat QC dumped into cold reservoir
o “Negative” work W- done by engine to bring gas to original W
state.

In a cyclic process, it is impossible to convert all the energy

extracted from an equilibrium system into work. Some part of this
energy must be transferred to a colder system.
 Internal combustion engines cycle consists 4 process

1. Burning of fuel (isothermal

expansion)
2. Fast expansion (adiabatic)
3. Compression to original
pressure (isothermal process)
4. Compression to original
temperature (adiabatic process)
 Carnot Heat Engine

Carnot heat engine takes gas through reversible

cyclic process consisting of 4 steps:

1. Isothermal expansion at T= TH
2. Adiabatic expansion from T= TH to T= TC
3. Isothermal compression at T= TC
4. Adiabatic compression from T= TC to T= TH
 Reversible/Irreversible Processes

𝑻𝒇 𝑽𝒇
Entropy: ∆𝑺 ≥ 𝟎 → ∆𝑺 = 𝒏𝑪𝒗 ln +nRln
𝑻𝒊 𝑽𝒊
This is 2nd law of thermodynamics
Heat Engines (Carnot)
𝑾 𝑻𝑪
𝑲= →𝟏−
𝑸𝑯 𝑻𝑯
 Chapter 6 Gas Power cycle

Gas Power Cycle: Heat engine in which working fluid remains in the gaseous system
throughout the cycle.
The performance of the cycle always measured in terms of efficiency.

o Otto Cycle
o Spark Ignition o The most efficient heat engine
o Diesel Cycle that can operate between two
o Brayton Cycle fixed temperature TH and TC is
o Gas Turbine called Carnot engine
o Rankine Cycle
 Carnot Cycle

Q-W=0 Q=W In addition,

we know that the efficiency
for a Carnot Cycle is:

𝑇𝐿
𝐾 𝑐𝑎𝑟𝑛𝑜𝑡 = 1 −
𝑇𝐻

Where K is thermal
o 1 to 2 Isothermal heat addition efficiency of Carnot cycle
o 2 to 3 Isentropic expansion
o 3 to 4 isothermal heat rejection
o 4 to 1 Isentropic compression
 Air-Standard Assumptions Terminology for Reciprocating Devices
o Air continuously circulates
in a closed loop and
behaves as an ideal gas
o All the processes are
internally reversible
o Combustion is replaced by
a heat addition process
from the outside
o Heat rejection replaces the
exhaust process
o Also assume a constant
value for Cp, evaluated at
room temperature
 𝑉𝑚𝑎𝑥 𝑉𝐵𝐷𝐶
Compression Ratio = 𝑟 = =
𝑉𝑚𝑖𝑛 𝑉𝑇𝐷𝐶

Mean Effective Pressure

Otto Cycle

(a) 1-2 Isentropic Compression

(b) 2-3 Constant Volume Heat Addition
(c) 3-4 Isentropic Expansion
(d) 4-1 Constant Volume Heat Rejection
Thermal Efficiency of the Otto Cycle
Apply First Law Closed System to Process 4-1,V = Constant
 Efficiency of the Otto Cycle
vs. Carnot Cycle
There are only two
temperatures in the Carnot
cycle
o Heat is added at TH
o Heat is rejected at TL
There are four temperatures
in the Otto cycle
o Heat is added over a
range of temperatures
o Heat is rejected over a
range of temperatures
 What is the fundamental behavior of diesel engines?
What happen if we use higher
compression ratio to gasoline o No spark plug
engine? o Fuel is sprayed into hot compressed air

o Premature Ignition Diesel Cycle

o Causes “Knock”
o Reduces the Efficiency
o Mechanically need a better
design

The only difference is in process 2-3

For any heat engine thermal efficiency is given by
rc is called the cutoff ratio – it’s
the ratio of the cylinder volume
before and after the combustion
process
 Why use the Diesel cycle?

The efficiency of the Otto cycle is always higher than the Diesel cycle
 Brayton Cycle

o The Brayton
cycle is the air-
standard ideal
cycle
approximation
for gas-turbine
engine.
o Let us assume
the working
fluid is air and
the specific
heats are
constant then we
will consider
cold-air-
standard cycle
 (a) 1-2 Isentropic Compression (in compressor)
(b) 2-3 Constant pressure Heat Addition
(c) 3-4 Isentropic Expansion (in turbine)
(d) 4-1 Constant pressure Heat Rejection

Thermal efficiency of Brayton cycle

 Thermal efficiency becomes

Conservation of energy for process 4-1

yields constant specific heats
 Regenerative Brayton Cycle

o The Brayton cycle, the turbine exit

temperature is greater than the compressor exit
temperature. Therefore, a heat exchanger can
be placed between the hot gas leaving the
turbine and the cooler gases leaving the
compressor. The heat exchange is called
regenerator or recuperate

We define the regenerator effectiveness eregen as the

ratio of the heat transferred to the compressor gases in
the regenerator to the maximum possible heat transfer
to the compressor gases.
 Regenerative Brayton Cycle

o For ideal gases using the cold-air-standard assumption with constant specific heats, the regenerator
effectiveness becomes

Using the closed cycle analysis and treating the heat addition and heat rejection as steady-flow processes, the
regenerative cycle thermal efficiency is

Notice that the heat transfer occurring within the regenerator is not
included in the efficiency calculation because this energy is not a heat
transfer across the cycle boundary.
Assuming an ideal regenerator eregen = 1 and constant specific heats, the
thermal efficiency becomes (take the time to show this on your own)
Regenerative Brayton Cycle

When does the efficiency of the air-standard Brayton cycle equal the
efficiency of the air-standard regenerative Brayton cycle? If we set
hth,Brayton
= hth, regen then

o Recall that this is the pressure ratio that maximizes the net work for the simple Brayton cycle and
makes T4 = T2. What happens if the regenerative Brayton cycle operates at a pressure ratio larger than
this value?

o For fixed T3 and T1, pressure ratios greater than this value cause T4 to be less than T2, and the
regenerator is not effective.
Regenerative Brayton Cycle

o The following shows a plot of the regenerative Brayton cycle efficiency as a function of the pressure
ratio and minimum to maximum temperature ratio, T1/T3.
 Chapter 7 Vapor Cycle

Carnot vapour power cycle, drawbacks as a

reference cycle, simple Rankine cycle; description,
T-s diagram, analysis for performance.
Comparison of Carnot and Rankine cycles. Effects
of pressure and temperature on Rankine cycle
performance. Actual vapour power cycles. Ideal
and practical regenerative Rankine cycles, open
and closed feed water heaters. Reheat Rankine
cycle.

Application of vapor power cycle

o Vapor power cycles are used in steam power plants. In a
power cycle heat energy (released by the burning of fuel) is
converted into work (shaft work), in which a working fluid
repeatedly performs a succession of processes. In a vapour
power cycle, the working fluid is water, which undergoes a
change of phase.
Chapter 7 Vapor Cycle
Rankine Cycle:
o The simplest way of overcoming the inherent practical difficulties of
the Carnot cycle without deviating too much from it is to keep the
processes 1-2 and 2-3 of the latter unchanged and to continue the
process 3-4 in the condenser until all the vapour has been converted
into liquid water. Water is then pumped into the boiler upto the pressure
corresponding to the state 1 and the cycle is completed. Such a cycle is
known as the Rankine cycle. This theoretical cycle is free of all the
practical limitations of the Carnot cycle.
 Chapter 7 Vapor Cycle
Rankine Cycle:

Figure (a) shows the schematic diagram for a simple steam power cycle which works on the principle of a Rankine cycle.
Figure (b) represents the T-S diagram of the cycle.

The Rankine cycle comprises the following processes. Process

a) 1-2: Constant pressure heat transfer process in the boiler
b) Process 2-3: Reversible adiabatic expansion process in the steam turbine
c) Process 3-4: Constant pressure heat transfer process in the condenser and
d) Process 4-1: Reversible adiabatic compression process in the pump.
 Chapter 7 Vapor Cycle
Rankine Cycle:

o Applying Steady flow energy equation (SFEE) to each of the processes on the basis of unit mass of fluid
and neglecting changes in KE & PE, the work and heat quantities can be evaluated.
o For 1kg of fluid, the SFEE for the boiler as the CV, gives,
o h1 + QH = h2 i.e., QH = h2 – h1 --- (1)
o SFEE to turbine, h2 = WT + h3 i.e., WT = h2 – h3 --- (2)
o SFEE to condenser, h3 ± QL + h4 i.e., QL = h3 – h4 --- (3)
o SFEE to pump, h4 + WP = h1 i.e., WP = h1 – h4 --- (4)

The pump handles liquid water which is incompressible i.e., its density or specific volume undergoes little
change with an increase in pressure.
For reversible adiabatic compression, we have Tds = dh – vdp; since ds = 0 . We have, dh = vdp
Since change in specific volume is negligible, ∆h = v ∆ P Or (h1 – h4) = v4 (P2 – P3)
Usually the pump work is quite small compared to the turbine work and is sometimes neglected. In that case,
h1 = h4
 Chapter 7 Vapor Cycle
Rankine Cycle:

o The efficiency of the Rankine cycle is presented graphically in the T-S

diagram
Chapter 7 Vapor Cycle
 Chapter 7 Vapor Cycle
o Carnot cycle has the maximum possible efficiency for the given limits of temperature. But it is not suitable in steam
power plants. Figure shows the Rankine and Carnot cycles on the T-S diagram.
o The reversible adiabatic expansion in the turbine, the constant temperature heat rejection in the condenser, and the
Reversible adiabatic compression in the pump, are similar characteristic features of both the Rankine and Carnot
cycles. But whereas the heat addition process in the Rankine cycle is reversible and at constant pressure, in the
carnot cycle it is reversible and isothermal.
Mean temperature of Heat addition
o In the Rankine cycle, heat is added reversibly at a constant pressure,
but at infinite temperatures. Let Tm1, is the mean temperature of
heat addition, so that area under 1s and 2 is equal to the area under 5-
6.
 Chapter 7 Vapor Cycle
o Effect of Boiler Pressure (Using Molliar Diagram i.e., h-s diagram)

i.e., Rankine cycle η depends on h2, h1 and ∆hS. From figure as

P1″′ > P1″ > P1′ for the fixed maximum temperature of the steam t1
and condenser pressure P2, Isentropic heat drops increases with
boiler pressure i.e., from the figure therefore it is evident that as
boiler pressure increases, the isentropic heat drop (∆h)S increases,
but the enthalpy of the steam entering the turbine decreases, with
the result that the Rankine η increases. But quality of the steam at
the exit of the turbine suffers i.e., x3″′ < x3 ″ < x3′, which leads to
serious wear of the turbine blades.
 Chapter 7 Vapor Cycle
o Effect of Super Heating (Using Molliar Diagram i.e., h-s diagram)

o The moisture in the steam at the end of the expansion may be

reduced by increasing the super heated temperature of steam t2.
This can be seen in figure where t2″′ > t2″ > t2′, but x3′ < x3″
<x3″′.
o It is, therefore, natural that to avoid erosion of the turbine blades,
an increase in the boiler pressure must be accompanied by super
heating at a higher temperature and since this raises the mean
average temperature at which heat is transferred to the steam, the
Rankine η increases.
 Chapter 7 Vapor Cycle
o Deviation of Actual Vapour Power cycles from Ideal cycle

o The actual Vapour power cycle

differs from the ideal Rankine
cycle, as shown in figure, as a
result of irreversibilities in
various components mainly
because of fluid friction and
heat loss to the surroundings.
 Chapter 7 Vapor Cycle
o Deviation of Actual Vapour Power cycles from Ideal cycle

o As a result of irreversibilities, a pump requires a greater work input, and a turbine produces a smaller work output.
Under the ideal conditions, the flow through these devices are isentropic. The deviation of actual pumps and turbines
from the isentropic ones can be accounted for by utilizing isentropic efficiencies, defined as

Ideal Reheat cycle: We know that, the efficiency of the Rankine cycle could be increased by increasing steam pressure
in the boiler and superheating the steam. But this increases the moisture content of the steam in the lower pressure
stages in the turbine, which may lead to erosion of the turbine blade. ∴The reheat cycle has been developed to take
advantage of the increased pressure of the boiler, avoiding the excessive moisture of the steam in the low pressure
stages. In the reheat cycle, steam after partial expansion in the turbine is brought back to the boiler, reheated by
combustion gases and then fed back to the turbine for further expansion.
 Chapter 7 Vapor Cycle
o In the reheat cycle the expansion of steam from the
initial state (2) to the condenser pressure is carried out
in two or more steps, depending upon the number of
reheats used.
o In the first step, steam expands in HP turbine from
state 2 to approximate the saturated vapour line
(process 2-3s). The steam is then reheated (or
resuperheated) at constant pressure in the boiler (or in
a reheater) process 3s-4 and the remaining expansion
process 4s-5 is carried out in the LP turbine.
o To protect the reheater tubes, steam is not allowed to
expand deep into the two-phase region before it is
taken for reheating, because in that case the moisture
particles in steam while evaporating would leave
behind solid deposits in the form of scale which is
difficult to remove. Also a low reheat pressure may
bring down Tm1 and hence cycle η. Again a high
reheat pressure increases the moisture content at
turbine exhaust. Thus reheat pressure is optimized.
Optimum reheat pressure is about 0.2 to 0.25 of initial
pressure.
 Chapter 7 Vapor Cycle
o In practice, the use of reheat gives a marginal increase in cycle η, but it increases the net work output by
making possible the use of higher pressures, keeping the quality of steam at turbine exhaust within a
permissible limit. The quality improves from X51 s to x5S by the use of reheat.
 Chapter 7 Vapor Cycle
o Ideal Regenerative cycle: The mean
temperature of heat addition can also be
increased by decreasing the amount of
heat added at low temperatures. In a
simple Rankine cycle (saturated steam
entering the turbine), a considerable part
of the total heat supplied is in the liquid
phase when heating up water from 1 to 11
, at a temperature lower than T2, the
maximum temperature of the cycle. For
maximum η, all heat should be supplied at
T2, and feed water should enter the boiler
at 11 . This may be accomplished in what
is known as an ideal regenerative cycle as
shown in figures (a) and (b).
 Chapter 7 Vapor Cycle
o The unique feature of the ideal regenerative cycle is that the condensate, after leaving the pump circulates
around the turbine casing, counter-flow to the direction of vapour flow in the turbine. Thus it is possible to
transfer heat from the vapour as it flows through the turbine to the liquid flowing around the turbine. Let us
assume that this is a reversible heat transfer i.e., at each point, the temperature of the vapour is only
infinitesimally higher than the temperature of the liquid. ∴The process 2-31 represents reversible expansion of
steam in the turbine with reversible heat rejection. i.e., for any small step in the process of heating the water
∆T (water) = - ∆T (steam) and (∆S) water = (∆S) steam. Then the slopes of lines 2-31 and 11 -4 will be
identical at every temperature and the lines will be identical in contour. Areas 1-11 -b-a-1 and 31 -2-d-c-31 are
not only equal but congruous. ∴, all heat added from external source (QH) is at constant temperature T2 and
all heat rejected (QL) is at constant temperature T3, both being reversible
 Chapter 7 Vapor Cycle

∴The net work output of the ideal regenerative cycle is less and hence its steam rate will be more. Although it
is more efficient when compared to rankine cycle, this cycle is not practicable for the following reasons. 1)
Reversible heat transfer cannot be obtained in finite time. 2) Heat exchanger in the turbine is mechanically
impracticable. The moisture content of the steam in the turbine is high.
Regenerative cycle:
 Regenerative cycle:

Since (Tm1)with regenerative > (Tm1)without

regenerative, the η of the regenerative cycle will be
higher than that of the Rankine cycle.

In the Rankine cycle operating at the given pressure P1

and P4, the heat addition would have been from state 7
to state 2. By using two stages of regenerative feed
water heating., feed water enters the boiler at state 11,
instead of state 7, and heat addition is, therefore from
state 11 to state 2.
 Regenerative cycle:

o Energy gain of feed water = energy

given off by vapour in condensation.
Heaters have been assumed to be
adequately insulated and there is no
heat gain from, or heat loss to, the
surroundings. In figure (a) path 2-3-4-
5 represents the states of a decreasing
mass of fluid. For 1kg of steam, the
states would be represented by the
path 2-31 -411-51 .