Technical Thermodynamics

Egon P. Hassel Prof. Dr.-Ing. habil. Dipl.-Phys.

Institute of Technical Thermodynamics Department of Mechanical Engineering and Shipbuilding University of Rostock, Germany Tel: +49 381 498 9400 email: egon.hassel (et) uni-rostock.de website: www.LTT-Rostock.de or http://web.me.com/egon.hassel December 23, 2009

CONTENTS

Contents
7 Pure materials and Clausius Rankine process 7.1 The complex behavior of the density of water with the temperature at constant 7.2 Water cooking at 1 bar . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.3 The boiling procedure of water . . . . . . . . . . . . . . . . . . . . . . . . . 7.4 Three dimensional diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.5 Vapor pressure diagram . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6 Denition of vapor content . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.6.1 Quantitative T-s-diagram and log(p)-1/T-diagram . . . . . . . . . . . 7.7 Properties of state of real uids . . . . . . . . . . . . . . . . . . . . . . . . . 7.8 Equations of state (EOS) with virial coecients . . . . . . . . . . . . . . . . 7.9 Realgasfaktor . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.10 Liquid vapor region . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7.11 Sketch of the most important h-s-diagram . . . . . . . . . . . . . . . . . . . 7.12 T-s-diagram with evaporation heat . . . . . . . . . . . . . . . . . . . . . . . 7.13 Mathematics: linear interpolation . . . . . . . . . . . . . . . . . . . . . . . . 7.14 Clausius Rankine process, classical power plant station process . . . . . . . . . 7.14.1 Exergy eciency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3 3 5 7 7 9 9 13 13 17 17 18 20 22 22 22 29

LTT-Rostock, Prof. Dr. Egon Hassel CONTENTS

LTT-Rostock, Prof. Dr. Egon Hassel CONTENTS

Chapter 7 Pure materials and Clausius Rankine process

7.1 The complex behavior of the density of water with the temperature at constant pressure

Pure materials are for example pure water or pure nitrogen. From such materials we know that they appear in three dierent phase states, as solids, as liquids or as gases. The most important substance of water we know as ice, liquid water and water vapor. Since all technical processes work with substances, we should know their behavior in order to design and understand these processes. As an impressive example of the complexity of the behavior of the properties of even seemingly simple substances, look at the density versus temperature for water at ambient pressure, gures 7.1 and is 7.2. We already notice here that the phase transition is an unsteadiness. At ambient pressure p and at t = 0 C two phases are present simultaneouly at the same time and with the same temperature T and the same pressure p, and T and p remain constant although heat is added or subtracted. In gure 7.2 the density of water at constant pressure, e.g. ambient pressure p = 1bar, between t = 100 C and t = 200 C is drawn qualitatively. During the process heat is added. We start at t = 100 C. The following special characteristics of water properties behavior are to be seen: 1. The solid body Ice behaves like a normal solid body, it expands with rising temperature. 2. During the phase transition (ice - > liquid) the water contracts unlike most materials, volume change is about 9 %. 3. Starting from t = 0 C the specic volume of the water decreases with rising temperature until a minimum with t = 4 C is reached, there the density of the liquid is largest. One recalls that this is called the anomaly of the water. This eect makes it possible for sh to survive in the winter if the lake above freezes over, but the water on the bottom t = 4 C is still liquid. 4. Starting from t = 4 C the density decreases with rising temperature, as with each other normal liquid. 5. At t = 100 C at 1 bar there happens the phase change (liquid - > vapor), with a volume increase of approximately a factor of 800. This is also an unsteadiness, with two phases, liquid and vapor, existing simultaneously with the same temperature and the same pressure in thermodynamic equilibrium. During the phase change the temperature and the pressure stays constant. 6. Starting from t = 100 C the water vapor behaves similar to any other gas, expanding with increasing temperature (at p = const). For very high temperatures the water vapor can be treated as an ideal gas, because the molecules interaction (potential) energies due to the van der Waals hydrogen binding forces are small in comparison to the kinetic energy due to the high temperature.

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

quantitative water and ice, density versus temperature

an under cooled liquid is still a liquid!

density kg/m!

ca. 9% volume increase

water
under cooled liquid

ice
!100C

!50C(= !58.0F) 0C(= +32F) 50C(= 122.0F) temperature in C and F

+100C

Figure 7.1: water density quantitative versus temperature, ice -> liquid

density water qualitative p = const e.g. 1 bar: ice, melting (0OC), anomaly (4OC), liquid, evaporation (100OC), vapor anomaly at 4 OC largest density

density qualitative (kg/m^3)

approx 1

kg/m3

approx 9% volume decrease ice -> liquid

approx 800-fold expansion with evaporation liquid -> vapor

temperature
-100C
-148F

0C
-32F

+100C
+212F

+200C
+392F

C/F

Figure 7.2: water density quanlitative versus temperature from -100 C to +200 C

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Water cooking at 1 bar

Isobaric boiling of water, p=1.0133 bar

heating 20 O C start of boiling 100 O C end of boiling 100 O C over heating 150 O C

boiling 100 O C

liquid
= vapor bubbles

vapor
= last liquid droplets

vapor ! gas

Figure 7.3: The isobaric evaporation of water at p=1,0133bar, scheme Conclusion from this: even such a common substance like water, which we might consider as simple, exhibits a very complex and strange behavior in its state variables dependence on temperature and pressure. And in oder to design and understand technical processes we should understand this behavior. Many materials behave similarly, so that in this basic course of technical thermodynamics water serves as a model substance for the other ones. The chapter is separated into two subsections A) The general behavior of pure materials, B) power station processes with water in the h s-diagram.

7.2

Water cooking at 1 bar

Before we start with this section, we want to observe the well known boiling procedure of water. This is similar to our water boiling in the morning for breakfast eggs or coee or tea. The air (oxygen gas and nitrogen gas) which is present can be neglected for these observations. From this experiment later on we are better able to understand the diagrams. See gure 7.3. The water from the water tap, state (1), has a temperature of t = 20 C perhaps, this state (1) is called undercooled liquid. With the heat of the stove plate the liquid is warmed up rst to t = 100 C, state (2), where the liquid begins to evaporate. From state (1) to state (2) the liquid expands a little bit. With further heating more and more vapor evolves. The vapor has a much larger specic volume than the liquid, the expansion is approximately 800-fold. Temperature and pressure remain constant during the entire boiling procedure, i.e. liquid and vapor are present simultaneously. State (3) is a state in the so called two phase region with liquid and vapor simultaneously. We add heat until all liquid water is evaporated, state (4), which is called saturated vapor. Starting from state (4) we have only water vapor which is like a real gas, approximately like an ideal gas if the pressure is 1 bar, that is the vapor expands with increasing temperature. LTT-Rostock, Prof. Dr. Egon Hassel Water cooking at 1 bar 5

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process
Isobaric boiling of water, p=1.0133 bar, T-v-diagram

T, p = const
liquid
2 3 4

vapor

two phase region

1

Figure 7.4: The isobaric evaporation of water at p=1,0133bar, T-v-Diagram State (2) is called boiling liquid or saturated liquid, state (4) is called condensing vapor or saturated vapor. This behavior is plottet in a T-v-diagram in gure 7.4 as an isobaric line. Conclusion: Even such a seemingly simple substance such as water already shows a very complicated behavior, which we want to be able to describe. The rst and second law of thermodynamics describe natural processes in general without making statements about material properties. In order to be able to use these relations practically, one needs additional data concerning the characteristics of the materials, which can be described in the thermal and caloric equations of state (EOS). The theory of the classical thermodynamics makes no declaration about these EOS. The equations of state (EOS) are the result of measurements. Between the thermal equation of state pV = mRT and the caloric equation of state dU = mcv dT the Gibbs fundamental relation exists:

T ds = du + pdv = dh vdp.

(7.1)

In general three phases are distinguished: gas, liquid and solid. The solid can occur further in dierent phases, e.g. diamond, graphite, amorphous carbon. The characteristics of material mixtures are still much more complex than that of pure materials, which we (nearly) only regard. From our observations so far, we want to show and to develop some new diagrams and characteristics and dene some new terms for pure substances. Fortunately the dierent diagrams look similar to each other and additionally they are also similar for dierent substances. Mostly in the course of studies we see diagrams of water, because water is the most important substance for us humans, naturally and technically, and thus it is also one of the best-investigated substance. For the equilibria of each phase of a pure material there is a thermal equation of state: f (p, v, T ) = 0. In a three-dimensional p v T -diagram, p as function of v and T , the function f (p, v, T ) = 0. represents gives a two dimensional surface p = p(v, T ), which we will show later. The tripel point (TrP) of water is the point of state of water in which water exists in all three phases simultaneously. 6 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel The boiling procedure of water

T-v-diagram of water

vapor
liquid

two phase region

Figure 7.5: T v diagramm of water with several isobaric lines. as ice, as liquid and as vapor. Tripel point of water: Ttrp = 273, 16K, ptrp = 0, 00611bar The critical point (kP) is the point in the diagrams (p v, T s, h s) which marks the maximum pressure above which no phase transition liquid to vapor can be detected. Critical point of water: Tk = 647, 3K, pk = 22, 115M P a, vk = 0, 00315m3 kg

7.3

The boiling procedure of water

Now we want to study the boiling of water in more detail, see again gure 7.3, and above all we want to extend it into the higher pressure range. First we want to show for the process form gures 7.3 and 7.4 a T-v-diagram with several isobaric lines, gure 7.5, and then also a p-v-diagram with several isotherms, gure 7.6. In gure 7.7 we see a p-v-diagram for a pure substance with isothermal lines and solid state area, it is not for water because the substance expands on the phase transition from solid -> liquid.

7.4

Three dimensional diagrams

The two-dimensional diagrams are only projections on a two dimensional area of the the respective thermodynamic functions, e.g. p = p(T, v). Remember: For a one component system we need exactly two independent variables of state for the exact description, each third variable is function of those two. In the next gure 7.8 an example of a three dimensional diagram for a pure substance (not water) is shown. It is not for water because it expands on phase transition from solid to liquid. One can follow the paths, i.e. isobaric processes A->F, G->I and L->M. LTT-Rostock, Prof. Dr. Egon Hassel The boiling procedure of water 7

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

p-v-diagram of water

vapor liquid

two phase region

Figure 7.6: p v diagramm of water with several isothermal ines.

p-v-diagram of water
according to H.D. Baehr, Hannover

Isothermal lines

vapor

solid
two phase region l-v

Figure 7.7: p v diagram of a pure substance (not water) with several isothermal lines. 8 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Vapor pressure diagram

p,v,T-plane of a pure substance (not water), according to H.D. Baehr, Hannover

thawing

melting

We can follow the path, A-F, or L-M, or G-I

see book of Baehr (Thermodynamik in German) for more on this

solid
p

sublimation

two phase

gas

This is not water, because the solid expands when it thaws.

desublimation

Figure 7.8: Three dimensional diagram of a pure substance (not water), the p-v-area is shown, according to H.D. Baehr, Thermodynamik, Springer Verlag.

7.5

Vapor pressure diagram

A further projection from the three-dimensional diagram is those of the so-called vapor pressure diagram, see gure 7.9, in which the vapor pressure as function of the temperature for a material is represented. The gure 7.9 is only one part of the complete area. A larger area is to be seen in gure 7.10. In this diagram also the boundary lines between solid and gas, and solid and liquid are drawn. One can see the tripel point and also the critical point. Also the dierence between the behavior of water and normal substances can be seen in the boundary line solid to liquid. And if we draw the vapor pressure curves in the form of ln(p) over 1/p they are (nearly) straight lines, see gure 7.11 in which the vapor pressure curves for Ar, N2 , CO2 and H2 O are shown. Among other things this is very favorable for the measurement procedure, because one needs only to measure very few points in order to draw the straight lines for sucient accuracy.

7.6

Denition of vapor content

As with each new chapter, after having observed the strange and complex behavior of even pure substances, we need a nomenclatur to handle it. First we dene some abbreviations: msolid = ms mliquid = ml mvapor = mv On the boiling-point line: mliquid,boiling = m On the line of saturated vapor: mvapor,saturated = m LTT-Rostock, Prof. Dr. Egon Hassel Vapor pressure diagram 9

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process
p -T- diagram, vapor pressure curve for water, in principle

liquid
gas
1.0133 bar

vapor pressure curve

100 C

Figure 7.9: Vapor pressure diagram for water p over T..

phase equilibrium in p-T-diagram

water

normal substance

solidifying
melting

liquid
condensing

krP

evaporating

solid
trP
desublimate

gas

sublimimate

Figure 7.10: Vapor pressure diagram p over T with solid state area. 10 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Denition of vapor content

11

vapor pressure curves as ln(p) versus 1/T

(according to H.D. Baehr, Hannover)

ln( p)

1 ! $ # 1000K & " %

1 T

Figure 7.11: Vapor pressure diagram for water.

definition of quality x = vapor contents 4 5

subcooled liquid

saturated liquid

2phase

saturated vapor

superhated vapor

heating until boiling point

definition of quality:

evaporation

overheating

x=

mvapor mliquid + mvapor

m '' m '+ m ''

Figure 7.12: To the denition of the vapor content or quality, denition of quality and boiling process. LTT-Rostock, Prof. Dr. Egon Hassel Denition of vapor content 11

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process
Definition of quality, example of isobaric evaporation of water
heating 20 O C
start of boiling 100 O C

boiling 100 O C

end of boiling 100 O C

over heating 150 O C

x1

x2 = 0

0 < x3
!!!!!!< 1

x4 = 1

x5

Definition of quality:

! x1 = not defined, x2 = 0, 0 " x3 " 1, x4 = 1, x5 = not defined

Figure 7.13: To the denition of the vapor content or quality, where is x dened. Denition of vapor content or quality: x= mvapor m = mliquid + mvapor m + m (7.2)

Only in the two-phase area the quality or vapor content is dened as x, see also gures 7.12, and 7.13. In gure 7.13 we see x qualitatively as follows: x1 = not dened x2 = 0., x3 0, 0001, x4 = 1. and x5 = not dened. In the gure 7.14 we see how an extensive state variable is the sum of the individual state variables of the dierent phases. One can deduce thus: V = V + V = m v + m v v= V m (7.3) (7.4)

V V v = m = m +m = (1 x) v + xv = v + x (v v )

(7.5)

x=

v v v v

(7.6)

v v h h s s u u x = = = = v v h h s s u u 12

(7.7) LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Properties of state of real uids

Definition quality: fraction of mass of vapor to total mass 1 2 3 4 5 quality:

13

V1 = mvliq

V3 = m3 'v3 '+ v3 ''v3 '' = m3 v 3

U, H, S the same procedure

Figure 7.14: To the denition of the vapor content or quality, extensive state variables.

7.6.1

Quantitative T-s-diagram and log(p)-1/T-diagram

Here we wish to show two additional diagrams, a quantitative T-s-diagram and a log(p)-h-diagram, see gures 7.15 and 7.16.

7.7

Properties of state of real uids

Now we know already the property behavior of real uids, that is real liquids and real gases, we know the evaporation and condensing processes, and the two phase region. On the other hand we are familiar with the ideal gas equation, pV = mRT , that is the thermal equation of state for ideal gases. We might wonder, if it could be possible, to derive a thermal equation of state (thermal EOS) which explains ideal gases and real gases in the liquid-vapor region simultaneously.
1

Johannes Diderik van der Waals, 1837-1923, see gure 7.17 found such an equation, and it is simple and it is based on mending the funamental assumptions we made for an ideal gas. The so-called van the Waals equation is simple and physically justied. The idea is as follows: There are two basic assumptions, which led to the ideal gas equation: 1. The molecules have no interaction force between them, if they are distant. This corresponds to the freedom of attractive or repulsive forces between the molecules. If we would consider interaction forces this would lead to an additional internal pressure.
1) (source: wikimedia commons, the copy-right of this image has expired because it was published more than 70 years ago without a public claim of authorship (anonymous or pseudonymous), and no subsequent claim of authorship was made in the 70 years following its rst publication, so the photo is public domain)
1

LTT-Rostock, Prof. Dr. Egon Hassel Properties of state of real uids

13

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

T-s-diagram water, quantitative, with isobaric, isochoric, isothermic lines

free according to H.D. Baehr, Thermodynamik, Springer Verlag)
100 bar

h=3500 kJ/kg
1000 bar
500 bar

0,01m 3 /kg
50bar

3000 kJ/kg
0,1m 3 /kg
10 bar

1,0 bar
0,1bar

10m 3 /kg

1000 kJ/kg

2000 kJ/kg

Figure 7.15: Quantitative T s-diagram for water with isobaric lines, isochoric lines, and lines for constant enthalpy.

log(p)-h-diagram for pure substance

gas

liquid
2phase

Figure 7.16: Qualitative ln(p)-h-diagram for a pure substance, which is used in cooling technology.

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Properties of state of real uids

15

Figure 7.17: Johannes Diderik van der Waals, 1837-1923, Quelle: wikimedia commons, copyright: see footnote 1 2. The sum of the volumes of the individual molecules is small in relation to the total volume of the container: Vi V
i

. It might be good idea to include the molecules volume into the thermal EOS.

Consequentely the van der Waals EOS is: p+ a (v b) = RT, v2 (7.8)

The term a/v 2 accounts for (weak) attractive or repulsive forces between the molecules, b accounts for the (small) volume of the molecules. The rsulting curves are shown in gure 7.18 and 7.19 as black isobaric lines, which continue into the two phase region as broken green curves. Values for a and b are tabulated for many substances and there are approximations for their determination from the critical values: (pcr, Tcr, Vcr). The parts a-b and d-e in the two phase region can be observed, the parts b-d is thermodynamically not feasible. We want to discuss the resulting curves: 1. Curve part a -> b, best see T-v-dia: imagine a liquid which is heated over a ame, say in a test tube in a students chemical lab. The liquid gets hotter and hotter untilit should start to evaporate, which ist refuses to do. Say the liquid is water at 1 bar, it gets e.g. to t = 105 Centigrade, and suddenly it separates in a boiling liquid, a saturated liquid, and vapor bubbles, which rapidly accelerate the liquid from the test tube, like in an explosion. Therefore it is a must to wear always safety gogles when working in chemistry lab. The liquid at 1 bar and 105 C ist called superheated liquid (from a-b is liquid) and can exit only under very undisturbed circumstances. 2. Curve part b -> d: best see p-v-dia: if by a small disturbance the volume increases by dv >0 the pressure would get larger by dp > 0, thus the expansion would increase which is a positive feed back loop and makes this region instable, does not exist. LTT-Rostock, Prof. Dr. Egon Hassel Properties of state of real uids 15

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process
van der Waals equation of state for real gasess van der Waals p-v-diagram

d
a
c

T2 T1 < T2

Figure 7.18: Van der Waals equation in p-v-diagram, green broken lines are van der Waals, straight black line is thermodynamic equilibrium.

van der Waals equation of state for real gasess van der Waals T-v-diagram

p2 p1 < p2

b
a c e

Figure 7.19: Van der Waals equation in t-v-diagram, green broken lines are van der Waals, straight black line is thermodynamic equilibrium. 16 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Equations of state (EOS) with virial coecients

17

3. Curve part d -> e, this branch is called under cooled vapor and is made use of e.g. in the Wilson cloud chamber and plays a very important role in meteorology and in the atmosphere. If we have air in between e d, it should have build rain droplets, but does not so, so it is still undercooled vapor. Until a disturbance happens and it separates in rain droplets and saturated vapor. This eect can show dierences of several degree on Centrigrade from under cooled point to saturated point. The values for a and b within the van der Waals equation are tabulated for dierent substances and one can estimate these also from the critical parameters (pkr , Tkr , Vkr ). The van that Waals equation of state has great theoretical importance particularly in statistic thermodynamics. The knowledge of the thermodynamic properties of materials is fundamental for the solution of engineering tasks, especially in the chemical industry and process engineering. For practical use mostly other EOS (not the vdW EOS) are applied.

7.8

Equations of state (EOS) with virial coecients

For practical use the van der Waals equation is not so often employed but one uses equations of state (EOS) with so called virial coecients. These are the result of more or less physically justied series expansions of p depending on powers of 1/v = which are tted to experimental results. For pure materials one makes a series expansion, e.g. the Kamerlingh Onnes equation of state: B C D E F + 2+ 4+ 6+ 8 v v v v v

pv = A +

(7.9)

with the so-called virial coecients A = RT , B = b1 T + b2 + b3 /T + b4 /T 2 + ., C =, D =, E =, F =. Values for the coecients are tabulated. There are many further equations of state in the literature, a good introduction is the work of Wagner and Span, Bochum, Germany, and of Kretzschmar, Zittau, Germany. For water EOS is published within the VDI Heat Atlas. Some more important EOS are: Beattie Bridgeman equation Benedict Webb ruby equation fair Kwong equation fair Kwong Soave equation Peng Robinson equation

7.9

Realgasfaktor

The deviation of the behavior of a real gas from that of an ideal gas can easily be estimeted with the help of the so called real gas factor: Z= pv RT (7.10)

For ideal gases Z = 1. An example of Z as a function of T and p for water is shown in gure 7.20. As result from the picture one can see that with low pressure or at high temperature Z 1, i.e. then the gas behaves with good approximation like an ideal gas. Low pressure and high temperature means in comparison to the critical values pkr , Tkr . LTT-Rostock, Prof. Dr. Egon Hassel Equations of state (EOS) with virial coecients 17

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

Z =
real gas factor ref: Perry)

pv RT

for water

H. Perry, Chemical Engineers Handbook, 5, 1973, according to K.F. Knoche, Technische Thermodynamik, Vieweg Verlag

Figure 7.20: Real gas factor for water in dependence on temperature and pressure, T and p are given as ratio to the critical values.

7.10

Liquid vapor region

In the liquid and gaseous state in thermodynamic equilibrium a material is homogeneous, each state is then called a phase. In the liquid vapor region the material heterogeneous, it consists of two separated phases. Here we want to study only those conditions in which the two phases are in thermodynamic equilibrium, that is they have the same pressure and the same temperature. The specic variables of state, e.g. u, h, v, s, are naturally dierent for the two phases. In this section we limit our study to the liquid vapor region and to pure water. We learned that for a pure substance in thermodynamic equilibrium we need exactly to independent state variables to describe the state completely. But because in the liquid vapor region T and p are coupled, we need another state variable, that is the quality or vapor content from above, x. Lets rst reconsider our denition from above: See gure 7.21, denition: 1. () stands for boiling liquid, thats saturated liquid, left boundary curve from the left hand side up to the critical point, v , h , s , m . 2. () stands for saturated vapor, right boundary curve from the critical point to the right, v , h , s , m , etc. The denition of vapor content or quality is: mv ml + mv m x = . m + m x = 18 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Liquid vapor region

liquid-vapor area

19

`
3

``

Figure 7.21: Liquid vapor region for water in p-v-diagram. See denitions of saturated liquid as () and as saturated vapor as (). Wet vapor is a mixture from saturated liquid and saturated vapor, which are in thermodynamic equilibrium. m m = with m = m + m + m m m (7.11)

x=

And for example the volume as extensive variable of state is the sum of the partial volumes of the liquid and vapor phase: V = V + V = m v + m v or for an arbitrarily selected state (3):
V3 = V3 + V3 = m3 v3 + m v3 3

(7.12)

(7.13)

And also V m m = v + v m m + m m + m V = (1 x)v + xv = v + x(v v ) m (7.14)

v=

v= with

(7.15)

LTT-Rostock, Prof. Dr. Egon Hassel Liquid vapor region

19

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process
liquid-vapor area: Law of opposite lever arms

Geometrical interpretation in p - v - diagram:

Law of the opposite lever arms

Figure 7.22: Rule of the opposite lever arms, a/b = m/m.

x=

From this we can see, the rule of the opposite lever arms: v v x m A = = = v v 1x m b (7.17)

m v v h h s s = = = m + m v v h h s s

(7.16)

See gure 7.22. Because in the h s, T s, p v-diagrams the mixture state is on the straight line between the points these formulas are identical also for s and h, e.g. see gure 7.23. Thus: v v x m A h h s s = = = = = v v 1x m b h h s s

and

(7.18)

Thus from the diagrams one can directly read distances with the help of a ruler and from that get the ratio of the liquid to the vapor mass and the enthalpy and entropy quantitatively. The values on the boader lines () and () are given also in tables for the liquid vapor region.

7.11

Sketch of the most important h-s-diagram

It is often required that one should draw a process quickly and qualitatively into a h-s-diagram. For this one should know how the isothermal and isobaric lines run in the diagram, see gure 7.24. Note especially the isothermal line behavior above the critical point and in the liquid region. 20 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Sketch of the most important h-s-diagram

21

liquid-vapor area: Law of opposite lever arms

p = const

Figure 7.23: Rule of the opposite lever arms in h-s-diagram.

h-s-diagram of water with p and t lines T T p p

Notice especially the course of the isothermal lines.

Figure 7.24: Sketch of h-s-diagram with isobaric and isthermal lines for water. LTT-Rostock, Prof. Dr. Egon Hassel Sketch of the most important h-s-diagram 21

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

7.12

T-s-diagram with evaporation heat

Denition of the heat of vaporization (evaporation enthalpy): r(T ) = h (T ) h (T ) (7.19)

r(p) = h (p) h (p) or r = h h = (u u ) + p(v v )

(7.20)

(7.21)

with u u - internal heat of vaporization, and p(v v ) - external heat of vaporization. A nice interpretation of this is to be seen in the T s-diagram. Generally according to the Gibbs relation it is: T ds = dh vdp If is p=const is valid: T ds = dh vdp = dh if T = is const is valid: T ds = dh vdp = dh = T (s s ) = h h = r (7.24) (7.23) (7.22)

The evaporation enthalpy in the T s-diagram is the rectangle surface under the isotherms T, see gure 7.25.

7.13

Mathematics: linear interpolation

Often we have to interpolate values from tables, that means intermediate values have to be found between the xed table values. Here is a simple example, see 7.26, 7.27 and 7.28, for more look at mathematics text books.

7.14

Clausius Rankine process, classical power plant station process

Modern life depends on electricity, think of the skript I am just writing, or all the pumps which drain the waste water continuously. Electricity in large quantities, say Giga Watts come from power plant stations, fueled with hard coal, brown coal, oil, natural gas or nuclear fuel. Most of these power plant stations, gas fueled are one exemption, heat and evaporate water in a cycle which then drives a steam turbine which then turn an electric generator which delivers electricity in a range of GW. A typical modern hard coal red power plant station delievers about 05 GW electricity. 22 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Clausius Rankine process, classical power plant station process

23

liquid-vapor area: Heat of vaporization

Surface = r = h ``- h `

Figure 7.25: T-s-diagram with heat of evaporation area.

linear interpolation

Figure 7.26: Mathematics, linear interpolation, I LTT-Rostock, Prof. Dr. Egon Hassel 23 Clausius Rankine process, classical power plant station process

24

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

linear interpolation

Figure 7.27: Mathematics, linear interpolation, II

linear interpolation

Figure 7.28: Mathematics, linear interpolation, III 24 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Clausius Rankine process, classical power plant station process
Clausius Rankine process Elements of a simple vapor power plant

25

exhaust gas
boiler

air + fuel

Condenser
ash
feed water pump

Figure 7.29: Clausius Rankine process, conguration diagram. The main parts of a modern power plant station are the boiler, the water cycle, the exhaust gas after treatment and the electrical turbine. Here we will condsider the main water cycle, the so called primary water cycle. A fundamental and basic water cycle, in which the important features can be studied, is the so called Clausius Rankine Cycle (CRC). It consists of just four parts and several assumptions are made for the principle cycle. In a real power plant station we have much more apparatus, but with our simple approach here, we can later on extend our analysis to the more complex systems without much trouble. We call a Clausius Rankine Process (CRP) the clock wise cyclic process which can be seen in gure 7.29. The corresponding h-s-diagram can be seen in the next gure 7.30. And an example of some real modern data, is given in gure 7.31. Rostock power plant station is currently the most modern hard coal station in Germany. First see gure 7.29. The principle clock wise cycle consists of four main aggregates working with pure water. All data are just example data from the Rostock power plant. Smaller and bigger plants exist. Starting from state point (1), which is undercooled liquid water at a pressure p1 < 1bar, the feed pump takes in the undercooled liquid water and pumps it to a pressure of e.g. p2 = 250bar, state point (2). In the vapor generator, or boiler, the liquid water rst is heated until it is saturated water (), is then evaporated until it is saturated vapor () and then it is over heated until state point (3). The heat inow e.g. is Q23 +1.5GW . A typical state (3) can be: p = 260bar, t = 545C, which is overheated water vapor. The hot vapor (3) ows into the turbine which creates mechanical power by rotation of the axle and then by use of a generator electrical power, wt34 0.5GW < 0. The water ow with low pressure and low temperature, state (4) then enters the condenser, where it is cooled down to the state (1) again. State (4) typically is in the liquid vapor region with a high vapor quality x. The heat ow Q41 < 0 goes as waste heat ow to the environment, e.g. to a river or in a cooling tower to LTT-Rostock, Prof. Dr. Egon Hassel 25 Clausius Rankine process, classical power plant station process

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LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

h-s-diagram for Clausius Rankine process

Figure 7.30: Clausius Rankine process, h-s-diagram.

Some technical data to hard coal power plant in Rostock

Electrical output power (gross/net): Net efficiency: boiler firing thermal input: vapor flow rate: Live vapor pressure (3): vapor temperature (3): additionally long-distance heat supply: max Efficiency with max. long-distance heating: Source: www. kraftwerk-rostock. de

553/509 MW 43,2% 1370 MW 1650 t/h 262 bar 545 C 300 MW 62%

On this site there are also beautiful functional diagrams

Figure 7.31: Clausius Rankine process, some data of an example of the hard coal red power plant station in Rostock, Germany. 26 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Clausius Rankine process, classical power plant station process

27

the atmosphere. Thus the process is closed. We want to draw a h s-diagram of the cyclic process now, let us see gure 7.30. First we draw an empty h-s-diagram of water with the boudary line of the saturated liquid, the critical point and the boundary line of the saturated vapor, and then isobaric lines, one for the high pressure, p2 and one for the low pressure, p4 . How many isobaric lines do we need? That depends on what assumptions we make for the pressure drop by dissipation in the heat exchangers from (2->3) and (4->1). If we consider these as frictionless, then we have no pressure drop there, and then we only need two isobaric lines, that is what we will do here. In principle we have the following informations about the cycle: 1st law for stationary ow processes (SFP): dh = q + wt . 2st law for stationary ow processes (SFP): ds = (q)/T + (wr /T = (q)/T + sirr . Table values and diagram values for the material variables like p, T, h, s, v, h, s, v, h, s and v. Thus, lets follow the process: process 1->2, feed pump: If the pump works adiabatically and frictionless, then ds = 0. If there is friction, then point (2) lies on the right hand side of point (1) and because of the 1st law for SFP, state (2) is over state (1). T ds = q + wdiss , dh = q + wt . Process 2->3, boiler or vapor generator: q > 0, wt = 0 => dh > 0. If no friction arises, the pressure remains constant, if friction arises, the pressure drops slightly. With a Clausius Rankine process mostly one regards the boiler as frictionless. If the water vapor is overheated, then point (3) lies on the right hand side and above point (2) on the isobaric line of p2 = p3 . process 3->4: turbine: See also chapter 4 in which we explained such an expansion in a turbine process in very detail. If the turbine is adiabatic and frictionless, then ds34 = 0. If some friction arises, then point (4) is on the right hand side of point (3), and because of the 1st law for SFP (4) is below point (3) dh < 0. process 4->1: Condenser: q41 < 0, wt41 = 0, dh < 0. If no friction arises, the pressure remains constant, if some friction arises, the pressure drops slightly. With the classical Clausius Rankine process one regards the condenser as frictionless. The vapor (4) becomes full condensed and somewhat undercooled (1). That meany the typical assumptions for the Clausius Rankine process are: the pressure drop in the vapor generator and condenser is neglected, the irreversibilities in the pump and in the turbine are considered. In the next gure ?? some typical data of the hard coal power plant station in Rostock, Germany, are shown. This is currently the most modern hard coal station in Germany. Now we can do some calculations with the help of the 1st and 2nd law. The total cyclic Clausius Rankine process If we regard the entire process as closed system, it follows: wt12 + wt34 = q23 + q41 (7.25)

The delivered work is the turbine work (wt34 < 0) plus the pump work (wt23 > 0) and is altogether negative: LTT-Rostock, Prof. Dr. Egon Hassel 27 Clausius Rankine process, classical power plant station process

28 W = wt12 + wt34 < 0 m

LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

wt,ges =

(7.26)

For all individual aggregates the 1st law for SFP is valid: 0 = h1 h2 + wt12 + q12 And the 2nd law for stationary ow processes reads: 0 = s1 s2 + q12 + serr T (7.28) (7.27)

With the frictionless evaporator and frictionless condenser T as thermodynamic mean temperature is:
s3

s2

T ds = Tm23 (s3 s2 )

(7.29)

The feed pump (1->2): The pump work is: wt12 = h2 h1 > 0 (7.30)

In oder to get q quality measure for the pump, we dene the isentropic pump eciency as ratio of the pumps real work to the minimum work which would be required in a reversible process (ds = 0, see also gure 7.30: minimumwork h2 h1 = 1 realwork h2 h1 (7.31)

p12 =

The pump work is small in the comparison with the turbine work: |wt12 | < |wt34 | (7.32)

The vapor generator: The vapor generator is assumed to be frictionless and thus an isobaric process. In reality the pressure drop can be several % of the input pressure. q23 = h3 h2 > 0 The adiabatic turbine The adiabatic turbine work is: wt34 = h4 h3 < 0 (7.34) (7.33)

We dene here also an isentropic turbine eciency, in order to measure the quality of the turbine, see again gure 7.30: 28 LTT-Rostock, Prof. Dr. Egon Hassel Pure materials and Clausius Rankine process

LTT-Rostock, Prof. Dr. Egon Hassel Clausius Rankine process, classical power plant station process realworkdone h4 h3 = 1 maximumworkpossible h4 h3

29 (7.35)

T 34 =

The condenser: In the condenser the remainder of the enthalpy of the ow is delivered as waste heat to the environment in oder to close the cyclic process. The condenser is assumed as frictionlessly and thus as isobaric: q41 = h4 h1 < 0 (7.36)

Clausius Rankine process altogether: The duty for the Clausius Rankine process altogether: wt,ges = wt34 + wt12 = (|wt34 | |wt12 |) < 0 wt,ges = wt34 + wt12 = h4 h3 + h2 h1 (7.37) (7.38)

The thermal eciency of the entire cyclic process is: th = |wt,ges | |h4 h3 | |h2 h1 | = <1 |q23 | |h3 h2 | (7.39)

7.14.1

Exergy eciency

As we have seen, the exergy is the availability of the energy, that is the part of an energy that is freely convertible into any other form of energy. Thus an exergy eciency is the ratio of the exergy coming out of a process or a machine in comparison to the exergy which is put in. Thus we dene the exergy eciency for the CRP as technical output work ow Wt in relation to the exergy ow which the boiler takes in, that is the exergy ow of stream ow (2) minus exergy ow of stream ow (1): m(e2 e1 ): p = Wt wt = m (e2 e1 ) e2 e1 (7.40)

e2 is the specic exergie of the water ow at (2), e1 is the specic exergie of the water ow at (1), e1 = h1 hu Tu (s1 su ) e2 = h2 hu Tu (s2 su ) e2 e1 = h2 h1 Tu (s2 s1 ) wt,ges = wt34 + wt12 = h4 h3 + h2 h1 p = h4 h3 + h2 h1 h2 h1 Tu (s2 s1 ) (7.41) (7.42) (7.43) (7.44) (7.45)

The end of chapter 7 pure materials and Clausius Rankine process LTT-Rostock, Prof. Dr. Egon Hassel 29 Clausius Rankine process, classical power plant station process