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Thermo notes from professor an entire course

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- Applied Thermodynamics, 3rd Edition
- First Law of Thermodynamics
- New Variational Lagrangian
- Chap1(v93)
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- lecture 2
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You are on page 1of 79

THERMODYNAMICS

W van Niekerk

2013

ii

Preface

Students can find textbooks in Thermodynamics quite intimidating. The rigorous derivation of

all the laws and equations can be quite complex. Add to that the abstract nature of many of

the concepts used and no wonder Thermodynamics is perceived as difficult. In this document

an effort is made to develop the laws and concepts in an easy to follow, concrete manner. It is

an first, introductory text.

The logical way to explain the conservation of energy is to first cover closed systems (the control

mass) combining heat, work and internal energy in the First Law. Using that as foundation,

the concept of enthalpy is developed and the conservation of energy in open systems (control

volumes) explained. Once the student understands the concept of energy conservation, the

concepts the student now needs to understand are that of reversibility and entropy - be it in

open or closed systems. Once the student is comfortable with reversibility and entropy he/she

should find it easier to understand real systems and the generation of entropy. This approach

is followed in this text and is shown schematically in Figure 1 below.

ii

Figure 1: Overview

But also in the smaller detail, the approach is different. When the First Law for closed systems

(the control mass) is introduced, initially only heat, work and internal energy are taken into

consideration. Potential energy very rarely is relevant during the implementation of the First

Law for closed systems. Examples where potential and kinetic energy are relevant, are done.

Contents

Preface

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . .

1.1 Properties . . . . . . . . . . . . . . . . . . . . . . . .

1.1.1 Temperature . . . . . . . . . . . . . . . . . .

1.1.2 Pressure . . . . . . . . . . . . . . . . . . . . .

1.1.3 Volume and Mass . . . . . . . . . . . . . . . .

1.2 Single phase systems . . . . . . . . . . . . . . . . . .

1.2.1 Ideal gases . . . . . . . . . . . . . . . . . . .

1.2.2 Real Gases . . . . . . . . . . . . . . . . . . .

1.2.3 Liquids and solids . . . . . . . . . . . . . . .

1.3 Two-phase systems . . . . . . . . . . . . . . . . . . .

1.3.1 Phase change . . . . . . . . . . . . . . . . . .

1.3.2 Quality . . . . . . . . . . . . . . . . . . . . .

1.4 Determining the phase of water . . . . . . . . . . . .

1.4.1 Temperature and pressure . . . . . . . . . . .

1.4.2 Pressure or temperature and specific volume

1.4.3 Temperature or pressure and quality . . . . .

2 Work and heat in closed systems

2.1 Closed and open systems . . . . . . . .

2.2 Work . . . . . . . . . . . . . . . . . . .

2.2.1 The Isobaric Process . . . . . .

2.2.2 The Isothermal Process . . . .

2.2.3 The Adiabatic Process . . . . .

2.2.4 The Isochoric Process . . . . .

2.2.5 Process with Spring Restrained

2.2.6 Non-equilibrium processes . . .

2.3 Heat transfer . . . . . . . . . . . . . .

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Piston

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iv

CONTENTS

3.1 Internal energy . . . . . . . . . . . . . .

3.1.1 Ideal gases . . . . . . . . . . . .

3.1.2 Perfect gases . . . . . . . . . . .

3.1.3 Real gases . . . . . . . . . . . . .

3.1.4 Two phase systems . . . . . . . .

3.1.5 Compressesed liquids . . . . . . .

3.1.6 Solids . . . . . . . . . . . . . . .

3.1.7 Determination of internal energy

3.2 The First Law for closed systems . . . .

3.2.1 Kinetic and potential energy . .

3.2.2 Sign convention . . . . . . . . . .

3.3 Adiabatic processes . . . . . . . . . . . .

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4.1 Enthalpy . . . . . . . . . . . . . . . . . . . .

4.1.1 Ideal gases . . . . . . . . . . . . . . .

4.1.2 Perfect gases . . . . . . . . . . . . . .

4.1.3 Real and condensible gases . . . . . .

4.1.4 Compressed liquids and solids . . . . .

4.2 The first law for steady state, open systems .

4.2.1 Shaft work . . . . . . . . . . . . . . .

4.2.2 Heat . . . . . . . . . . . . . . . . . . .

4.2.3 Kinetic energy . . . . . . . . . . . . .

4.2.4 Potential energy . . . . . . . . . . . .

4.2.5 Common open systems . . . . . . . . .

4.3 Calculating heat transfer using specific heats

4.3.1 Compressed Liquids and Solids . . . .

4.3.2 Gases . . . . . . . . . . . . . . . . . .

4.4 Unsteady state processes . . . . . . . . . . . .

5 Reversible Systems

5.1 Reversibility and Irreversibility . .

5.2 Entropy . . . . . . . . . . . . . . .

5.3 Determination of Entropy . . . . .

5.3.1 Ideal gases . . . . . . . . .

5.3.2 Perfect gases . . . . . . . .

5.3.3 Real and condensible gases

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53

CONTENTS

5.4

5.5

5.6

Reversible processes . . . . . . . . . . . . . .

5.5.1 Reversible adiabatic processes . . . . .

5.5.2 Reversible processes with heat transfer

5.5.3 Reversible heat engines . . . . . . . .

Enthalpy revisited . . . . . . . . . . . . . . .

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6 Real Systems

6.1 Entropy generation in real systems . . . . . . . . .

6.1.1 Friction . . . . . . . . . . . . . . . . . . . .

6.1.2 Unrestrained expansion . . . . . . . . . . .

6.1.3 Heat transfer over a temperature difference

6.2 The significance of entropy generation . . . . . . .

6.3 Entropy in real systems . . . . . . . . . . . . . . .

6.3.1 Entropy transfer with heat. . . . . . . . . .

6.3.2 Internally reversible systems . . . . . . . . .

6.3.3 Internally irreversible systems . . . . . . . .

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ii

CONTENTS

Chapter 1

1.1

Properties

Substances have properties that are used to identify and describe them. You should be familiar

with four properties from everyday life: temperature, pressure, volume and mass. We measure

the amount of milk by volume and meat by mass. We quantify the hotness or coldness of

air by measuring its temperature. Pressure gives an indication of the force necessary to contain

a fluid.

We distinguish between intensive and extensive properties. Temperature is an intensive property

as its value does not depend on the amount of matter of the substance. A cup of water can be

at 20 C as well as a drop of water. Volume and mass are extensive properties. The mass and

volume of a substance is directly proportional to the amount of matter making up the substance.

A cup of water cannot have the same mass as a drop of water.

Another characteristic of properties is that the value of a property is not dependent on the history

of the substance. We cannot deduct from the temperature at the present moment whether the

temperature was higher or lower at an earlier stage.

1.1.1

Temperature

to K, add 273.15. This means 50 C is the same as 323.15K. It also means that a temperature

difference expressed in degrees Celsius is numerically the same as the difference expressed in

Kelvin. The lowest possible temperature is 0K. Temperature is an intensive variable.1

Temperature can also be measured in F . T [ F ] = 1.8T [ C] + 32. This means that 100 C = 212 F . The

absolute temperature associated with F is Rankine. The temperature in [R] is obtained by adding 459.67 to the

temperature in [F ]

1.1.2

Pressure

P =

F

A

With F in [kN ] and A in [m2 ], P will be in [kN/m2 ]=[kP a]. Pressure is an intensive variable.

Other common pressure units are:

atmosphere (1atm = 101.325kP a) and

bar (1bar = 100kP a)

Absolute or total pressure

The total pressure is the total force exerted on a surface divided by the area of the surface.

In a gas, the force exerted on a surface is due to the collision of the gas molecules against the

surface. There is a limit at how low total pressure can be. If no force is exerted on a surface the

total pressure is zero. The pressure of a complete vacuum is zero because there are no molecules

colliding with the surface of the container. Absolute pressure (Pabs ) is the pressure measured

above this zero point. The value of total pressure can never be negative.

Atmospheric pressure

Atmospheric pressure (Patm ) is the total pressure caused by the weight of the atmospheric air.

This pressure varies according to location and weather patterns. The average value at sea-level

is 101.325kP a. The average atmospheric pressure for Potchefstroom is 87.0kP a with 99% of

the values between 86.0kP a and 88kP a. The average atmospheric pressures for a few major

cities in South Africa are given in Table 1.1.2 It is clear that the height above sea level plays a

dominating role in determining the average value. Atmospheric pressure is also called ambient

pressure.

Table 1.1: Average atmospheric pressure for a few cities in South Africa.

City

Kimberley

Polokwane

Pretoria

Potchefstroom

Bloemfontein

Johannesburg

1230

1262

1350

1351

1395

1700

88.5

88.3

87.5

87.0

86.7

83.5

Gauge pressure

Gauge pressure (Pg ) is the difference between the pressure inside the vessel and outside. The

pressure outside is usually equal to atmospheric pressure but for a vessel submerged in water

2

1.1. PROPERTIES

such as a submarine, the pressure outside may differ from the atmospheric pressure.

Pg = Pabs Patm

If the total pressure of a fluid is lower than the atmospheric pressure, the gauge pressure will

be negative and when it is higher, it will be positive. Except when specifically stated that it

is a total or absolute pressure gauge, the pressure displayed by a pressure gauge is the gauge

pressure. We use a pressure gauge at the petrol station to measure the gauge pressure of the air

in the tires of our cars.

Example

Assume you have inflated the spare tyre of your car to a gauge pressure of 200kP a on the

Highveld where the atmospheric pressure on that day is 85kP a. The absolute (or total

pressure) inside the spare tyre is now 285kP a. You now drive to the sea where the atmospheric pressure on that day is 101kP a. What is the gauge pressure of the spare tyre now?

Solution

If the spare tyre does not leak, the mass of air inside does not change. Let us assume the

volume stayed the same as well as the temperature. Therefore the absolute pressure also

remained the same (this can be shown to be true by using the Ideal Gas Law which is done

later), but the gauge pressure would have dropped to 184kPa. You will have to inflate the

tyre somewhat if you want to use it now.

Hydrostatic Pressure

The pressure exerted by a liquid column with a constant density, is given by the equation:

P =

gh

1000

Example

Assume you go down a mine shaft 1000m deep. Calculate the pressure exerted by a column

of air 1000m high. Assume the air has a density of 1kg/m3 .

Solution

1 9.81 1000

= 9.81kP a

1000

This is in the same range as the change in pressure you will experience traveling from the

Highveld to the coast. The density of the air will change due to the significant change in

pressure - so the assumption of constant air density can be questioned. How will you account

for the change in air density?

P =

Example

A manometer is connected to a pipe filled with air as shown in the figure. The manometer

is filled with mercury. The density of the mercury can be taken as 13600kg/m3 . The height

(h) is 0.2m and the atmospheric pressure 87kP a. Calculate the absolute and gauge pressure

inside the pipe.

Solution

The pressure exerted by the column of mercury is:

Pmercury =

= 26.68kP a

1000

The pressure on the surface of the mercury exposed to the atmosphere is equal to 87kP a.

In the other leg of the manometer, at the same elevation, the pressure will also be 87kP a.

Moving upwards from that elevation to the surface of the mercury, will cause a drop in total

pressure. The density of the air is very low, therefore it can be assumed that the pressure

inside the pipe is uniform. Therefore:

Pabs,inside = 87 26.68 = 58.32kP a

The gauge pressure is 26.68kP a. From the figure it is also clear that the pressure inside

the pipe is lower than the pressure inside, therefore it makes sense that the gauge pressure

has a negative value.

1.1.3

In thermodynamics, volume and mass are usually combined to form a new property: specific

volume (v). Specific volume is the total volume divided by the total mass v = V /m [m3/kg].

Specific volume is an intensive property. Density () is the inverse of specific volume.3

Example

A cup holds 250m` of boiling hot water at 95 C. The mass of the water is 240.4g. Calculate

the specific volume in [m3 /kg] and the density in [kg/m3].

Solution

Specific volume is the volume divided by the mass: v = V /m. First determine the values of

V and m.

1`

1m3

1000m` 1000`

= 250 106 m3

1kg

m = 240.4g

1000g

= 240.4 103 kg

v = 250106/240.4103

V = 250m`

= 0.00104m3/kg

and = 1/v = 961.5kg/m3

Sometimes the density of a substance is given relative to a reference substance. Then it is called

relative density or the somewhat misleading term, specific gravity (SG). In the case of liquids

(and often solids) the reference substance is usually water at a pressure of 101.3kP a and 4 C

with a density of 1000kg/m3 . The density of mercury is often taken as 13.6. This means its

density is 13600kg/m3

Let us see how P, T and v are interdependent.

1.2

The term phase refers to a quantity of matter that is homogeneous throughout in both chemical

composition and physical structure. Homogeneity in physical structure means that the matter

is all solid, or all liquid, or all gas. An oil-water mixture consists of two liquid phases - a water

phase and an oil phase. They are both liquids but their chemical compositions differ. The

three phases of water are shown in Figure 1.2 below. The three phases are separated by phase

boundaries with zero thickness.

For single-phase substances, we can alter the values of two intensive properties independently.

For instance, consider water at 100kP a and 50 C (indicated by the ) We can increase the

3

In order to know whether answers you get during calculations are realistic, it is important that you remember

typical values for the variables you will encounter in Thermodynamics. The density of water is approximately

1kg/` or 1000kg/m3 while that of atmospheric air is approximately 1kg/m3 and the specific volume approximately

1m3 /kg.

temperature a few degrees without the water changing phase (starting to boil). We can also

reduce the temperature of the steam (shown by the ) a few degrees without the steam changing

phase (condensing).

Because we can change the value of two intensive properties independently we say a single-phase

substance has two degrees of freedom.4 It means that once we have specified the values of two

independent intensive properties the state of the system is fixed and the values of other intensive

properties are also fixed. The state of the substance is simply the condition of the substance

as described by its properties. If we heat up water, we say its state has changed because its

temperature has changed. There are different ways in which to determine the value of the other

properties.

1.2.1

Ideal gases

An ideal gas is a hypothetical gas whose molecules/atoms do not attract or repulse each other

and collide elastically with each other and the walls of the container. They are point particles

occupying negligible space. At high temperatures and low pressures,5 the density of gases are

low (the particles will occupy negligible space) and the kinetic energy of the particles much

higher than any possible inter-particle interactions and under these conditions gases are often

considered as Ideal Gases obeying the Ideal Gas Law. In this law, pressure, temperature and

specific volume are combined in one equation: (P v = RT ). R is the ideal gas constant. Its units

are [kP a m3 kg 1 K 1 ] and it has a specific value for every substance as shown in the table

below.6 Tables with the values of the ideal gas constant for different substances can be found

in literature.[1, Table A.5]

4

The number of degrees of freedom are determined by the Gibbs Phase Rule. See Cengel [2, p.759]

As a rule of thumb, a gas can be considered ideal if its temperature is twice its critical temperature and its

pressure half its critical pressure. Critical pressure and temperature are explained in Paragraph 1.3.1

3

6

In literature, the units of R are usually given as [kJ/(kgK)]. This is the same as [(kP am )/(kgK)].

5

Substance

Air

Steam

Helium

R [kP a m3 kg 1 K 1 ]

0.287

0.4615

2.0771

It is clear from the Ideal Gas Law that once we know what the temperature and pressure are,

we can calculate the specific volume using the Ideal Gas Law. In fact, the value of all other

intensive properties (density, viscosity, internal energy etc) ) can now be determined. Knowing

the values of any two variables (P, T ; P, v; T, v) enable us to calculate the value of all other

intensive properties and we say the state is fixed.

Example

Consider air at 25 C and 101kP a. Calculate its specific volume and the mass of 1m3 of air.

Solution

RT

P

0.287 298.15

=

101

= 0.8475m3/kg

v=

m=

V

v

1

0.8475

= 1.180kg

=

Make sure of the units when using the Ideal Gas Law. Temperature is in Kelvin, pressure is

the absolute pressure in kP a and specific volume is in m3 /kg. In the case of gases like air in

everyday use and Helium, the Ideal Gas Law is quite accurate. Usually we do not use the Ideal

Gas Law for steam.7

7

Optional textbook reading: Cengel [2] discuss the question: Is water vapor an ideal gas? and Compressibility factor - a measure of deviation from Ideal Gas Behaviour. See also paragraphs 3.6 and 3.7 in Sonntag [1]

on the same topics.

1.2.2

Real Gases

Super-heated steam is usually considered to be a real gas and the specific volumes at different

temperatures and pressures are tabulated in tables known as the steam tables. These are

available in hard copy or as software.

Example

Find the tables for super-heated steam at the back of your textbook.[1, Table B.1.3] (Note

that water refers to the chemical H2 O and is not an indication of the phase. We talk of

solid water, liquid water and water vapor when we refer to the solid, liquid or gas phases.)

Determine the specific volume of steam at 5000kP a and 350C. (0.05194m3/kg).

Now use the Ideal Gas Law to determine the specific volume (0.0575m3/kg). You can

see there is a significant difference between the two values. At low pressures and high

temperatures, the agreement will be better. We will not worry at the moment about how

high is high or how low is low as we will not use the Ideal Gas Law for steam. Even though

you can find the ideal gas constant for steam and other real gases in the tables giving the

ideal gas properties of gases, the Ideal Gas Law is only used for these substances under

special conditions. For instance atmospheric air contains some water vapor and this water

vapor is ususally assumed to obey the Ideal Gas Law.

Example

Steam at 5000kP a has a specific volume of 0.054m3/kg. Find the temperature of the steam.

Solution

You will note that 0.054m3/kg lies between the specific volumes at 350 C and 400 C. You

need to interpolate to find the required temperature. (367.5C)

1.2.3

Liquids below their boiling temperature and above their melting temperature(compressed or

sub-cooled liquids) and solids below their melting points are also single phase systems. Because

their molecules are so densely packed, pressure does not have a big influence on their volume.

Liquids and solids are therefore usually considered to be incompressible and that their volume

depends only on temperature. The density of liquids and solids at a single temperature (or

sometimes as function of temperature) can be found in textbooks [1, Table A.3, A.4]. In the

steam tables the properties of liquid and solid water (ice) as function of temperature AND

pressure are tabulated.

Example

Find the table for compressed water in the back of your textbook.[1, Table B.1.4] Find the

specific volume of water at 20 C and 500kP a. (0.001002m3/kg)

Now find the specific volume at the same temperature but at 5000kP a. (0.001000m3/kg)

Note that the specific volume stayed essentially constant. The assumption that liquid water

is incompressible is therefore a good assumption.

1.3

Two-phase systems

We will first consider a system consisting of liquid water and water vapor.

1.3.1

Phase change

If we heat up water enough it will start to boil it will undergo a phase change. It is instructive

to study some of the events that occur as a pure substance undergoes a phase change. Consider

water at 101.325kP a in a piston-cylinder assembly. The water is at 20 C, a temperature lower

than the boiling point and therefore it is a single-phase system. It has two degrees of freedom.

The temperature and the pressure can be varied independently without the water changing its

phase. The water is heated while the pressure remains constant at 101.325kP a. The volume

increases slightly as the water is heated and the temperature rises.(Assume the combined effect

of the cylinder and the ambient pressure is 101.325kP a and the piston is frictionless and can

therefore move to accommodate any increase in volume.)

At the boiling point (100 C), vapor starts to form and a two-phase system results. Even though

more heat is added, the temperature will remain constant. With the addition of more heat

only more vapor forms. It is no longer possible to vary temperature and pressure independently

without the system changing phase. If we increase the pressure on the system (by putting on

additional weights on the piston) the vapor will condense, release heat, and a single-phase system

will result once more. If we resume heating at this higher pressure, the temperature will rise to

a higher value before vapor will start to form again. As long as heat is added to a two-phase

system all the liquid will eventually vaporize and a single phase - a saturated vapor, will result.

If the saturated vapor is heated, its temperature will rise and super-heated vapor will form. A

super-heated vapor is also known as a gas. This behavior is shown in Figure 1.3 below. The

constant pressure heating of water will show as a horizontal line on a P v diagram (Figure

1.7).

If the pressure is high enough, no phase separation will take place. The liquid will change from a

liquid-like phase to a gas-like phase without two phases forming. You can see this happening in

Figure 1.3 at 40000kP a. The minimum pressure where no phase separation takes place, is called

the critical pressure. The temperature at the critical pressure is called the critical temperature.

The critical pressure of water is 22.09M P a and the critical temperature 374.14C.

The constant pressure heating of water can also be shown as a vertical line on a T-P phase

diagram (Figure 1.2) The the liquid-gas phase boundary in Figure 1.2 ends in the critical point.

10

As long as two phases are present, the system is at the saturated state. The liquid is called

saturated liquid and the gas, saturated vapor. The temperature is the saturation temperature

and the pressure, the saturation pressure or vapor pressure. The relationship between saturation

pressure and saturation temperature is shown in Figure 1.4

It is clear from this graph that the equilibrium pressure is a unique function of temperature. For

a two-phase mixture, temperature and pressure are no longer independent. Once the pressure

(or temperature) is specified, the temperature (or pressure) and the specific volumes of the

saturated vapor and the saturated liquid are fixed. This seems to imply that two phase systems

have only one degree of freedom because all the variables are fixed once one variable is fixed.

This is true for saturated vapor only and saturated liquid.

Example

Find the saturation pressure, specific volume of saturated water vapor and specific volume

of saturated liquid water at 100 C. (101.325kP a; 1.6729m3/kg; 0.001044m3/kg)

11

In general we need to know the relative amount of liquid and vapor. We therefore need another

variable bringing to two the number of variables necessary to define the state completely. The

second variable can be specific volume or a variable that we will call quality.

1.3.2

Quality

For a saturated liquid-vapor mixture, the quality (x) is the ratio of the mass of vapor to the

total mass of the two-phase mixture:

x=

mvapor

mliquid + mvapor

The value of the quality varies from zero to unity. For a saturated liquid, x = 0, and for

a saturated vapor, x = 1. Quality is only defined for the saturated condition.8 Using the

saturation tables and the definition of quality, the specific volume of a two-phase liquid-vapor

mixture can be determined:

v = (1 x)vf + xvg

(1.1)

Example

Determine the pressure and specific volume of water at 100 C with a quality of 0.7.

Solution

Because the quality has a value between zero and one, we know it is a two-phase mixture

and the pressure will be the saturated pressure at 100 C, 101.3kP a. The specific volume of

the two phase mixture is calculated using Equation 1.1 and the volumes of saturated liquid

and saturated vapor at 100 C. ( 1.171343m3/kg)

It is also possible to get liquid/solid equilibrium and vapor/solid equilibrium. It is also possible

to get equilibrium between three phases - vapor, liquid and gas. It is the triple point and a pure

substance has only one triple point.

The slope of the solid/liquid equilibrium line for water on a pressure-temperature graph is

slightly negative. This means liquid water under pressure will freeze at a lower temperature

than water under a lower pressure. The slope is positive for substances that contracts upon

freezing.

If the behavior of any substance is plotted on three perpendicular axes, one each for temperature,

pressure and specific volume, a three dimensional shape results as shown in Figure 1.5 below.

1.4

We have four variables that can be used to fix the state of a substance: Pressure, Temperature,

Specific volume and quality. In order to determine the values of the unknown variables once the

8

This means that x can never have a value bigger than unity such as 1.2. If you ever calculate x and find it is

bigger than 1, you have made a mistake somewhere!

12

state is fixed, we need to know the phase (solid, liquid or gas) of the substance. Once we know

the phase, we know which table (compressed liquid, saturated liquid, super-heated vapor) to

use. Let us look at common combinations of variables used to fix the state and how to determine

the phase.

1.4.1

We determine the phase by comparing the specified temperature to the saturation temperature

at the specified pressure and comparing the specified pressure to the saturation pressure at the

specified temperature. In effect this means plotting the state on a PressureTemperature Phase

diagram. Only three phases are possible when the pressure and temperature are specified: solid,

liquid and gas. The lines separating the phases as in Figure 1.6 has zero thickness and the state

will either be a solid OR a liquid OR a vapor. The phase boundary between liquid water and

solid water (ice) is almost vertical.

Consider water at 100kP a and 50 C. The specified temperature is lower than 99.62C, the

saturation temperature at 100kP a and the specified pressure higher than 12.34kP a, the saturation pressure at the specified temperature. This means it is a compressed liquid as can be

seen from the position of the in Figure 1.6. The quality is undefined and if we assume an

incompressible liquid, the volume of the substance is the same as that of the saturated liquid at

50 C, 0.001030m3/kg, which can be read from the tables for saturated water.[1, Table B.1.2]

Consider water at 100kP a and 150 C. Its pressure is lower than 475.9kP a, the saturation

13

pressure at the specified temperature and its temperature is higher than 99.62C, the saturation

temperature at the specified pressure. This means it is a super-heated vapor as can be seen by

the position of the in Figure1.6. Again the quality is undefined and the specific volume can

be read from the super-heated water vapor tables, 1.93636m3/kg

1.4.2

Heating water at a constant pressure (lower than the critical pressure) will first result in a

saturated liquid, then the a two-phase mixture and then a super-heated vapor. The P-v phase

diagram is shown in Figure 1.7. The phase is determined by comparing the specific volume of

the system with the specific volume of the saturated vapor and saturated liquid at the known

pressure or temperature.

Water at 1000kP a and 0.0005m3/kg is a compressed liquid because its specific volume is smaller

than that of the specific volume of the saturated liquid at the same pressure. It is also clear

from the position of the in Figure 1.7. As the specific volume of a compressed liquid does not

change much with changes in temperature at lower values of temperature as can be seen in

Figure 1.3, it may be difficult to obtain an accurate value for temperature from specified values

of pressure and specific volume. For a compressed liquid, quality is undefined.

Water at 100kP a and 0.01m3/kg is a two-phase mixture as its specific volume lies between that

of the saturated liquid and saturated vapor at 100kP a. It is also clear from the position of the

in Figure 1.7. Its quality can be calculated from Equation 1.1 using the specific volume of

the saturated liquid (0.001043m3/kg), and the saturated vapor (1.694m3/kg) at 100kP a to obtain

a value of x = 0.005291. The temperature is the saturation temperature at 100kP a, 99.62C.

Water at 100kP a and 4.02781m3/kg is a super-heated vapor as its specific volume is larger than

that of a saturated vapor at the specified pressure. It is also clear from the position of the in

Figure 1.7. Its temperature can be determined from the super-heated water tables. In this case

the temperature can be read directly from the tables (600C), but in general, interpolation will

be necessary. Quality is undefined for a super-heated vapor.

14

When the temperature and specific volume are specified, the phase must first be determined

comparing the specific volume to the specific volumes of the saturated liquid and vapor at the

specified temperature - in effect by plotting the state on a T v diagram (Figure 1.3).

1.4.3

The quality of a saturated liquid is 0 and for a saturated vapor, 1. As quality is undefined for a

sub-cooled liquid and super-heated vapor, if the quality is specified, it means it is a two-phase

mixture and the temperature (or pressure) for the specified pressure (or temperature) can be

read from the tables for saturated water and the specific volume determined from Equation 1.1.

Chapter 2

Thermodynamics is the study of energy and energy conversion. Often we are interested in the

conversion of heat into shaft work. The burning of coal or nuclear fission generates heat. This

heat is converted into shaft work which can readily be converted into electricity in a generator.

We will study the different ways of converting heat into work and the limits to this conversion

later. In this chapter we will only look at how work is performed in a closed system. Then we

will also introduce heat transfer.

2.1

An important step in any analysis is to define the system we want to study. We distinguish

between open and closed systems. An open system is a properly selected region in space.

It usually encloses a device with mass flowing in and out of the device, such as a hair dryer,

a boiler or turbine. A closed system consists of a fixed amount of mass. No mass can cross

the boundaries of a closed system. A piston-cylinder arrangement is the most common closed

system. We encounter piston-cylinder arrangements in internal-combustion engines, the engine

of steam locomotives and reciprocating air compressors. The piston-cylinder arrangement in an

internal combustion engine is only a closed system during the compression stroke and during

the power stroke. During the other strokes one of the valves is open to either allow the air/fuel

mixture to flow into the cylinder or the combustion products to flow out of the cylinder. The

system boundary separates the system from the surroundings and has zero thickness. Energy

in the form of heat can cross the boundaries of open and closed systems and the system can

perform work or work can be done on the system.

We begin our discussion on work and heat transfer with closed systems. As a closed system

transforms from one state to another, it passes through an infinite number of intermediate states.

We assume that the deviation from equilibrium of these states are infinitesimal. This means

that there are no pressure and temperature gradients in the system and that a single value exists

for all properties of the system at any specific instant. In other words the pressure has a specific

value, temperature has a specific value and specific volume has a specific value at any moment

during the process. Changing form one state to another is called a process. We will encounter

15

16

several types of processes e.g. an isothermal process, where the temperature of the system stays

constant or an isochoric process where the volume stays constant.

2.2

Work

If a force of magnitude F is necessary to move a weight a distance s, the work is given by the

product: W = F s. Consider a gas inside a piston cylinder setup as in Figure 2.1. The gas

is heated, causing the volume to increase.

The magnitude of the work performed by the system in the process of going from state 1 to

state 2, is given by:

W =

F dx

(2.1)

The force is equal to the pressure of the gas multiplied by the area of the piston. It is usually

easier to work with the identical formulation of Equation 2.1:

Z 2

Wout =

P dV

(2.2)

1

This work is called boundary work because it is performed at the boundary of the system. If

pressure is measured in kP a and volume in m3 , work is in kJ. Work done by the system on the

environment (volume increases) will be a positive number while work done by the environment

on the system (volume decreases) will be a negative number. To determine the magnitude of

W , a relationship is required between the gas pressure at the moving boundary and the volume

of the system. In real processes this relationship may be difficult or even impossible to obtain

because of pressure gradients in the system or an unknown relationship between pressure and

volume. Different process paths between the two states are possible.1

1

Work is said to be a path function because the path followed determines how much work is performed. A

property on the other hand, is a point function, as its value does not depend on the path followed to get to its

present state.

17

2.2. WORK

For a few special processes, the relationship between pressure and volume can be expressed as

a simple mathematical equation. Assuming an quasi-equilibrium process, the pressure inside is

uniform and we can use a single value.

2.2.1

the volume will increase but the pressure inside will remain constant because the force exerted

on the system by the combined effect of the weight of the piston and the atmosphere does not

change during the process. P is therefore a constant and can be taken out of the integral sign

in Equation 2.2 and the equation for work becomes:

Wout = P (V2 V1 )

The process can also be presented graphically:

The work performed is equal to the area under the graph. Sometimes calculating the area under

the graph is the only way to calculate the magnitude of work.

2.2.2

If the volume is increased while the system is kept at a constant temperature (by adding heat)

and if the Ideal Gas Law (P = mRT/V ) is assumed, then the process path on a P-V graph will be

an hyperbole as shown in Figure 2.3. In general Equation 2.2 can be integrated by substituting

P from the Ideal Gas Law to give an equation for Wout :

Wout = mRT `n

V2

V1

18

Example

One kilogram of air at 25 C and 100kP a in a piston cylinder arrangement is compressed

slowly to a pressure of 200kP a. Heat is released at a sufficient rate to keep the temperature

constant during the process. Calculate the work.

Solution

The initial and final volumes can be calculated using the Ideal Gas Law: V1 = 0.8557m3

and V2 = 0.4278m3

Wout = mRT `n

V2

V1

= 1 0.287 298.15 `n

0.4278

0.8557

= 59.3kJ

The value is negative because work was performed on the air in order to raise its pressure.

In order to have a positive numerical value, the answer is reported as:

Win = 59.3kJ

Consider the isothermal expansion of steam. Steam cannot be assumed to be an ideal gas and a

convenient number of intermediate points (A and B) on the P -V diagram must be determined

and the area under the P-V curve determined numerically as shown in Figure 2.4.

19

2.2. WORK

2.2.3

In an adiabatic process, the system is well insulated so that no heat transfer takes place between

the system and the environment. If ideal gas behavior can be assumed and if the specific

heats (Paragraph 3.1.2) for the gas can be assumed constant (usually the case for the

mono-atomic gases He, Ar, Ne and Kr), the relation between pressure and volume during a

quasi-equilibrium process, is given by the following equation.2

PV k = c

(2.3)

The exponent k is equal to the ratio of the specific heats Cp and Cv . Its value can be found in

a table of ideal gas properties.3 The numerical value of the constant (c) for each process will

be different and must be determined from the conditions at some stage of the process for

instance the initial conditions P1 and V1 . This equation gives a relationship between pressure

and volume and Equation 2.2 becomes:

Wout = c

V2

V1

c

1k

V k dV

1k

1k

V2

V1

If a gas is compressed, the kinetic energy of the particles is increased by the approaching boundary much like a cricket ball being hit by a bat and the temperature of the gas rises. The

temperature of a gas that is expanded adiabatically, drops. The reason is that the particles

colliding with the expanding boundary, must perform work to move the boundary and transfer some of their kinetic energy to the moving boundary and therefore the temperature drops.

2

3

Sometimes is used instead of k.

20

constant. Although there is no heat transfer, there is energy transfer in the form of work.

2.2.4

In an isochoric process the volume stays constant and no work is performed. The area under a

the curve of an isochoric process drawn on a P -V diagram is zero.

2.2.5

If the piston is restrained by a linear spring, the P -V relationship of the process will be a

straight line. The area under a straight line is easily determined. The work can be determined

by drawing the process on a graph and calculating the area under the P-V line.

2.2.6

Non-equilibrium processes

In all the previous cases we assumed quasi-equilibrium processes - therefore uniform conditions

prevailed inside the system. Although this is often a good assumption, there are cases where it

is clearly not a valid assumption. In order to calculate the work done in such cases, integrate

Equation 2.1 using the external force acting on the system.

Example

Air at 25 C and 600kP a is contained in a piston cylinder arrangement with a cross sectional

area of 0.1m2 . The initial volume of the air is 1m3 . The mass of the piston is 0.1kg. The

atmospheric pressure is 87kP a. The piston is kept in position by a pin as shown in the

sketch. The pin is removed and the piston moves rapidly upward until it hits the stops.

The final volume is 3m3 . Calculate the work.

Solution

The combined effect of the weight of the piston and the atmospheric pressure means the

piston will exert a pressure of 96.81kP a on the air once it is free to move. This is the

pressure necessary to lift the piston and push away the atmosphere. The pressure exerted

by the air on the piston will be more than 96.81kP a. The moment the pin is removed the

pressure difference acting on the piston will cause the piston to accelerate upwards. The

21

piston will come to a standstill against the stops and the kinetic energy of the piston will

be converted into heat and sound. The work performed by the air is therefore

Wout = 96.81(3 1) = 193.62kJ

2.3

Heat transfer

Heat is defined as the form of energy that is transferred across the boundary of one system to

another system, at a lower temperature, by virtue of the temperature difference between the

two systems. A substance does not contain heat. Heat is only identified as it crosses the system

boundary. In actual fact the heat transfer takes place because the particles of the two systems

collide with each other. The particles of the hotter substance has higher molecular energy than

the particles of the colder substance. During a collision, some of the energy of the hot particle

is transferred to the cold particle. This increases the kinetic energy of the cold particle and

causes the temperature of the colder substance to rise. So heat transfer is actually kinetic

energy transfer on the molecular level. The heat that enters the system ends up increasing the

kinetic energies of the molecules and/or atoms of the system it entered. Temperature gives an

indication of the average kinetic energy of the particles of a substance the higher the kinetic

energy, the higher the temperature.

22

Chapter 3

We have already encountered work and heat as two forms of energy. In order to complete the

picture, another type of energy, internal energy, must be taken into consideration. These three

forms of energy will later be combined in the First Law of Thermodynamics.

3.1

Internal energy

Consider the heating of one kilogram of Helium in a rigid stationary container from 300K to

600K. The heat necessary is 1558kJ. No work was performed as the volume stayed constant and

the system remained stationary. Therefore the energy added to the system as heat, is absorbed

by the molecules of the gas. It increased the kinetic energy of the individual Helium atoms. To

name three:1

Translational kinetic energy

Rotational kinetic energy

Vibrational kinetic energy

The sum of all these microscopic energies is called the internal energy of a substance. It can be

shown that specific internal energy is a property. The symbol for specific internal energy

is u and its units are [kJ/kg]. The total internal energy of a system is U [kJ] and is equal to

m u. Because specific internal energy is a property, it is one of the variables that can be used

to fix the state of a substance. For a single phase system it means if we know the value of the

internal energy and either the value of temperature or pressure or specific volume, the state is

fixed and the value of the other properties can be determined.

The change in internal energy is calculated using the following equation [1, Equation 14.30]:

P

du = Cv dT + T

P dv

T v

(3.1)

1

Optional textbook reading. A more elaborate discussion of molecular forms of energy is given in par 2.6 of

Sonntag [1]

23

24

Where Cv is the constant volume specific heat. It is defined as the amount of heat necessary to

raise the temperature of a substance (at constant volume) by one degree.

3.1.1

Ideal gases

For an ideal gas it is assumed that the atoms or molecules do not attract or repulse each other.

Therefore there is no energy associated with inter-particle interactions. The distance between

particles is therefore irrelevant from an energy point of view. This means that the internal

energy of an ideal gas is only made up of the kinetic energies of individual particles and that

internal energy is not influenced by changes in density or pressure. The same is clear from

Equation 3.1. For an ideal gas P/T is equal to R/v and the term in the square brackets reduces

to zero. The change in internal energy for an ideal gas is therefore only dependent on the change

in temperature and can be calculated as follows:

Z T2

u2 u1 =

Cv dT

(3.2)

T1

To avoid having to integrate Equation 3.2 every time, the internal energy of ideal gases as

function of temperature (relative to a reference temperature Tref where the value of uref is set

to a chosen value), is tabulated as function of temperature.2 A table giving the internal energy

of air under the assumption of ideal gas behavior, is given in Borgnakke and Sonntag, Table

A7.1 [1].

Example

Calculate the temperature and specific volume of air at 200kP a with a specific internal

energy of 315.64kJ/kg.

Solution

From the table of the ideal gas properties of air [1] it can be determined that the temperature

corresponding to the given internal energy is 440K. The Ideal Gas Law can now be used to

calculate the specific volume: 0.6314m3/kg

Note that because of the assumption of ideal gas behavior, internal energy and temperature

are no longer independent and both cannot be specified to fix the state of the system.

Therefore u can only be used in combination with P and v.

The internal energy is independent of pressure, therefore there is only one column - giving the value of internal

energy for the tabulated values of temperature. The reference to pressure that usually appears in the heading of

such tables, is because the values of entropy, a property we have not encountered yet, is calculated at a certain

pressure, usually 100kP a.

25

3.1.2

Perfect gases

Figure 3.1: Cv values for Helium, Air and Steam (at two pressures)

From Figure 3.1 it is clear that the Cv of Helium stays essentially constant.3 In this text it

will be assumed that the Cv of the mono-atomic gases (Helium, Argon, Neon and Krypton), is

independent of temperature and that they obey the Ideal Gas Law. They are then collectively

called Perfect Gases. Equation 3.2 is now easily integrated to give the change in internal

energy for perfect gases:

u2 u1 = Cv (T2 T1 )

(3.3)

Example

Helium at 400kP a and 300 C is heated to 600 C while the pressure changes to 500kP a.

Determine the change in volume and the change in specific internal energy.

Solution

Using Equation 3.3 and the Ideal Gas Law:

u2 u1 = Cv (T2 T1 )

= 3.116 (600 300)

= 934.8 kJ/kg

3

In order to reduce the range of the y-axis, the units of Cv in Figure 3.1 is in

values with the right units in calculations.

kJ/kmolK .

26

R T2 R T1

P2

P1

2.0771 873.15 2.0771 573.15

=

500

400

= 0.651 m3/kg

v2 v1 =

The value for Cv found in tables is usually at a specific temperature but for a Perfect

Gas can be used at any temperature.

Even though this is not a constant volume process, Equation 3.3 is still valid. It is

valid for any perfect gas for any process: isobaric, isochoric, unspecified.... and can be

used to calculate the change in internal energy as long as the change in temperature

is known.

For a perfect gas, it is only possible to calculate the change in internal energy. This

means that the internal energy of a perfect gas does not have a value that can be used

to define the state. For perfect gases it is therefore necessary to use two of the other

three intensive properties (P, T, v) we are familiar with at the moment to define the

state.

As a perfect gas is a special kind of ideal gas, a change in pressure has no effect on

(the change in) internal energy.

The temperature difference calculated in C is the same as the temperature difference

calculated in Kelvin.

In the Ideal Gas Law, the temperature must be in Kelvin.

3.1.3

Real gases

For real gases, inter-particle distance is important because there may be energy associated with

inter-particle interactions (attraction or repulsion). From Table 3.1, the influence of pressure on

the internal energy of steam at 400C is clear.

Note that at low pressures, internal energy does not vary much with pressure. This is because

at low pressures, the steam molecules are far apart and the energy associated with their interaction, small. As the pressure rises to higher values and especially close the critical point, internal

energy is very sensitive to pressure. For a real gas it is necessary to know the value of two

variables to fix the state. Any two of the variables we have encountered thus far (Temperature,

Pressure, specific volume or specific internal energy) can be used.

27

Table 3.1: Influence of pressure on the specific internal energy of steam at 400 C.

Pressure (kP a)

10

100

1000

10000

25000

3.1.4

2968.9

2967.9

2957.3

2832.4

2430.1

For two-phase systems, pressure and temperature are no longer independent. For a saturated

liquid (x = 0) and a saturated vapour, (x = 1) the value for internal energy can be read directly

from the table for saturated water at the appropriate temperature or pressure. Note that the

internal energy of the saturated liquid at 0.01C is taken as zero.

For a saturated two-phase mixture, a calculation must be done. Quality (x) has already been

defined as the mass of vapor in a 1kg two-phase mixture. Quality can now be used to calculate

the internal energy of a two-phase mixture from the internal energy of the saturated liquid (uf )

and the saturated vapour (ug ) as follows:

u = (1 x)uf + xug

3.1.5

Compressesed liquids

The internal energy for compressed (or sub-cooled liquids) as function of temperature and pressure can be found in the steam tables. For incompressible substances, pressure will not affect

inter-particle distances and it usually assumed that the internal energy of sub-cooled liquids and

solids are not affected by pressure as shown in Table 3.2.

Table 3.2: Influence of pressure on the specific internal energy sub-cooled water at 100 C.

Pressure (kP a)

101.325

1000

10000

419.0

418.7

416.1

The internal energy for liquid water is therefore assumed to be only a function of temperature.

This means that the internal energy for liquid water can be read from the tables for saturated

water. For example the internal energy of water at 10M P a and 100 C is assumed to be equal

to the internal energy of saturated liquid water at 100 C even though the saturation pressure

is only 101.325kP a.

28

3.1.6

Solids

Usually constant specific heats are assumed for solids. Then the change in internal energy can be

calculated using Equation 3.3. However, because of the small change in volume during heating,

the values of Cv and Cp are essentially equal and often no distinction is made between the two

or only Cp is tabulated. This is discussed in more detail in Paragraph 4.3.1

3.1.7

Once the value of two independent properties are known the state is fixed and the value of the

other properties can be determined. Let us consider a few examples where internal energy is

involved.

Temperature and pressure.

The three phases of water as function of pressure and temperature are shown in Figure 1.6. The

first step is to determine the phase as explained in Paragraph 1.4.1 by determining the position

of the state relative to the phase boundaries.

Example

Determine the specific internal energy and specific volume of water at 100kP a and 50 C.

Solution

From the position on the phase diagram ( in Figure 1.6), it is clear that it is a compressed liquid. Assuming that uT ,P = ufsat@T : u = 209.3kJ/kg and also for volume,

v = 0.001012m3/kg . Quality is not defined for a compressed liquid.

Example

Determine the specific internal energy and specific volume of water at 100kP a and 150 C.

Solution

The state is indicated by the in Figure 1.6. From the position on the phase diagram, it

is clear that it is a super-heated vapor. From the tables for super-heated water vapor, we

can read the values for u = 2582.75kJ/kg and v = 1.93636m3/kg . Quality is not defined for a

super-heated vapor.

Note that on a P-T diagram, the state can never lie on the line separating the phases. The

line has zero thickness and therefore, for a specific temperature and pressure, the phase will be

either a liquid or a vapor.

Temperature or pressure and internal energy

The phase is determined by comparing the internal energy of the system with the internal

energy of the saturated vapor and saturated liquid at the specified pressure or temperature. If

the specified value for internal energy falls inside the dome , it is a two phase mixture and the

temperature is the saturation temperature. The quality can now be determined and from the

quality, the specific volume.

29

Example

Determine the temperature, specific volume and quality of water at 200kP a with an internal

energy of 2808.6kJ/kg.

Solution

The specified internal energy is bigger than the internal energy of saturated vapor at 200kP a,

2529kJ/kg and therefore it is a super-heated vapor. From the tables for super-heated water

vapor at 200kP a, the temperature that corresponds with the specified internal energy, is

300 C. The specific volume is 1.31616m3/kg. Quality is not defined for a super-heated vapor.

Example

Calculate the internal energy at 100kP a of a two-phase water mixture with a quality of 0.2.

(835.1kJ/kg)

Example

Determine the pressure of steam at 200 C with an internal energy of 2656kJ/kg

Solution

The specified value for internal energy is bigger than than the internal energy of saturated

vapor at 200 C, 2595kJ/kg and it is therefore a super-heated vapor. From the tables for

super-heated steam, it is clear that the internal energy of steam at 200 C and 100kP a

is bigger; and the internal energy at 200 C and 200kP a smaller than the specified value,

2656kJ/kg. The pressure of the system must therefore be between 100kP a and 200kP a.

Interpolation is therefore required. (156kP a).

30

3.2

The First Law simply states that energy cannot be destroyed or created merely converted

from one form to another. In a coal fired power station, heat is converted into work and

electricity. The First Law gives the relation between the three forms of energy encountered so

far heat, work and internal energy. Consider the closed system in Figure 3.3 undergoing a

process. Usually the substance contained in the piston-cylinder arrangement is taken as the

system. Heat is added to the system, it expands and raises the piston, performing work.

Work

Heat

State 1

State 2

The First Law states that energy is conserved. This means that the energy in the beginning,

the total internal energy U1 , plus the energy transferred to the system, the heat Qin , must equal

the the work done by the system, Wout , plus the energy in the system at the end of the process,

the total internal energy U2 . In mathematical terms:

U1 + Qin = Wout + U2

or:

Qin = m(u2 u1 ) + Wout

Example

One kilogram of steam in a piston-cylinder arrangement is at 200 C and 300kP a. The steam

is heated to 400 C in a constant pressure process. Calculate the heat that must be added

in order for the process to take place as described.

Solution

The First Law is used: Qin = m(u2 u1 ) + Wout

The work performed in a constant pressure process:

Wout = P (V2 V1 ) = 300(1.03151 0.71629) = 94.57kJ Done by system

The First Law now becomes:

Qin = (2965.53 2650.65) + 94.57 = 409.45kJ Required by system

Note that less than 25% of the energy added as heat is converted into work.

31

3.2.1

Whereas internal energy is on a microscopic level, the system can also undergo changes in energy

on a macroscopic level. If the center of gravity of the system changes height in a gravitational field

or changes velocity because of interactions between the system and the environment, the energy

associated with these changes must be taken into consideration and the First Law becomes:

2

Qin

m(V 2 V 1 ) mg(Z2 Z1 )

= U2 U1 +

+

+ Wout

2000

1000

where V is the velocity of the center of gravity of the system (in m/s) and Z is the height of the

center of gravity of the system (in meters). Usually the changes in kinetic and potential energy

are much smaller than the other terms and can safely be ignored. But there are instances where

it must be taken in to consideration:

Example

A lead bullet at 20 C traveling at 250m/s comes to a complete standstill against a target

plate. Calculate the temperature of the bullet after impact.

Solution

The bullet will exchange heat with the target plate but let us calculate the temperature

before any heat transfer takes place. Therefore it is an adiabatic process and 1 Q2 = 0.

The volume of the bullet will change with the change in temperature, doing some work

against the atmosphere. As can be seen from the thermal expansion coefficient for lead

( = 0.00003283K 1) the change in volume will be small and therefore it is assumed that

Wout is negligible. Assuming that the specific heat of lead is independent of temperature

and pressure, the change in internal energy is given by u = Cv T (from Equation 3.1).

The First Law becomes:

2

V1

Cv (T2 T1 ) =

2000

The specific heat of lead at 25 C is 0.13kJ/kgK .[1, Table A.3] Therefore the temperature of

the bullet after impact is 260 C. If the bullet traveled at the speed of sound ( 300m/s), it

would have reached its melting temperature (326.9C).

The two assumptions should now be checked. With the final temperature known, the change

in volume can be calculated as well as the change in specific heat. It is left to the reader to

do.

Example

A vertical piston/cylinder arrangement with a cross sectional area of 0.002m2

(D = 50.46 mm) contains 1kg saturated liquid water at 100kP a. The water is va-

32

porized at constant pressure until saturated vapor results. Calculate the heat required.

Solution

The height of the column of the liquid water will be 0.521m and the height of the vapor

column will be 846m. The center of gravity in each case is height/2. The setup is stationary

so the kinetic energy does not change and the First Law becomes:

Qin

Z2 Z1

+ P (v2 v1 )

= m (u2 u1 ) + g

1000

846 0.521

+ 100(1.693 0.001)

= (2506.06 417.3) + 9.81

2 1000

= 2088.7 + 4.147 + 169.2

= 2262kJ

It is clear that even with this extreme change in elevation of the center of gravity, that the

contribution of the change in potential energy is still small relative to the other terms.

3.2.2

Sign convention

Equation 2.1 gives the work done BY a system undergoing a process from state 1 to state 2:

Wout =

V2

P dV

V1

If work is performed BY the system (the volume increases), the value of Wout will be > 0 and if

work is done ON the system, the value of Wout will be < 0. In this text, Wout will be changed

to Win to ensure that the numerical value is > 0.

The heat transfer for an Ideal Gas undergoing a iso-choric process from state 1 to state 2, is

given by:

Q=m

T2

Cv dT

T1

If heat is ADDED to the system, the value of Q will be > 0, and if heat is RELEASED by

the system the value of Q will be < 0. This is true for other processes also. In this text the

appropriate subscript (in or out ) will be used to ensure that the value of Q is always > 0.

3.3

Adiabatic processes

The first law can be used to derive Equation 2.3 for an adiabatic process for a perfect gas.

PV k = c

33

which is the same as:

P2

=

P1

V1

V2

k

Q = dU + W

For an adiabatic process Q = 0, for an ideal gas, dU = mCv dT and for a quasi-equilibrium

process, W = P dV . This gives:

mCv dT = P dV

Dividing the left hand side of the equation by mRT and the right hand side by P V , the following

equation results for a Perfect Gas:

V1

Cv T2

ln

= ln

R

T1

V2

Which can be written as:

T2

T1

Cv

R

V1

V2

T2

P2 V2

=

T1

P1 V1

The last two equations can be combined to give:

P2

P1

Cv

R

Cv

V1 ( R

V2

+1)

Noting that that Cp Cv = R and after some manipulation, the following equation results:

P2

=

P1

V1

V2

Cp

Cv

V1

V2

k

which is the equation we set out to derive. From the above it also follows that:

T2

=

T1

P2

P1

k1

k

V2

V1

1k

v2

v1

1k

34

Chapter 4

An open system allows mass flow across its boundaries. Mass flow rate is measured in [kg/s].

Many of the systems engineers work with, are open systems. For instance the turbines, boilers

and pumps in large-scale power generation plants are open systems. A turbine performs shaft

work at a certain rate and the units of shaft work are [kJ/s] which is the same as kilo-Watts, [kW ].

The heat transfer rate is also measured in [kW ]. The energy content of a flowing substance is

given by enthalpy.

4.1

Enthalpy

Consider a pipe connected to a container. A fluid is flowing in the pipe and into the container.

The pressure of the container remains constant at P . A pressure P is therefore necessary to

push the fluid into the container. The work necessary to move one kilogram of fluid against

this pressure of P , is P v [kJ/kg]. This is called flow work. The rate at which work must

be performed to push the fluid into the container is mP

v [kW ]. The rate at which internal

energy is entering the container with this fluid, is mu

[kW ]. As Pressure and Specific volume

are both properties it is convenient to group flow work and internal energy together to form a

new intensive property, enthalpy (h):

h = u + P v [kJ/kg ]

(4.1)

The change in Enthalpy is calculated using the following equation:[1, Equation 14.28]

v

dh = Cp dT + v T

dP

T P

(4.2)

We now consider the the determination of enthalpy for Ideal gases, Perfect gases and Real and

condensible substances.

35

36

4.1.1

Ideal gases

The enthalpy of an ideal gas is not dependent on pressure because the internal energy of an ideal

gas is not dependent on pressure and P v = RT so h = u + RT and pressure does not appear

in this equation. It also follows from Equation 4.2. For an ideal gas, (v/T )P = R/P and the

term in square brackets reduces to zero. The change in enthalpy of an ideal gas can therefore

be calculated by performing the following integration:

Z T1

h2 h1 =

Cp dT

(4.3)

T2

The amount of heat necessary to raise by one degree, the temperature of one kilogram of a

substance in a constant pressure process (without phase change) is defined as the constant

pressure specific heat:

1 Q

Cp =

m T p

where Cp is the specific heat , Q the amount of heat in [kJ] and T the temperature of the

substance in Kelvin or Celsius. Because work is done when heating a gas at constant pressure,

more heat must be supplied to raise the temperature of a gas at constant pressure than would

have been the case if the volume stayed constant - therefore Cp > Cv . Also Cp Cv = R.

Equations for Cp for various ideal gases are available in literature [1, Table A.6] and can be

used in Equation 4.3 to calculate the change in enthalpy [1, Example 5.8]. In order to simplify

matters, the enthalpy for various ideal gases relative to a reference temperature Tref where href

was set equal to a chosen value, were calculated and are available in literature. Air is usually

assumed to be an ideal gas and its enthalpy as function of temperature can be found in literature

[1, Table A 7.1].

4.1.2

Perfect gases

In this text it will be assumed that the specific heats of mono-atomic (He, Ne, Ar) are not

dependent on temperature.1 It will also be assumed that they obey the Ideal Gas Law and

Equation 4.3 becomes:

h2 h1 = Cp (T2 T1 )

(4.4)

It is however now only possible to calculate the change in enthalpy.

4.1.3

If a substance is condensible under the process conditions or the ideal gas assumption is not

valid, enthalpy is a function of phase, temperature and pressure and its value found in tables.

The phase of the substance must first be determined (compressed liquid, saturated liquid/vapor,

two-phase or super-heated). The Pressure-Enthalpy diagram is shown in Figure 4.1. Note that

the enthalpy is also relative to a reference point (in the case of water, the triple point) where

1

37

4.1. ENTHALPY

enthalpy is taken to be zero. The quality is used to calculate the enthalpy of a two phase mixture

(in the same way as the internal energy of a mixture) as follows:

h = xhg + (1 x)hf

4.1.4

Because of the small value of v for liquids and solids, the P v term Equation 4.1 is much smaller

than u, so the change in enthalpy with pressure is also small and it can be assumed that the

enthalpy of a compressed liquid (and solid) is the same as that of a saturated liquid (and solid)

at the same temperature - as long as the difference between the pressure and the saturation

pressure at the temperature is not too large.

To simplify matters even further, constant specific heats can be assumed for liquids and solids2

- as long as no phase change takes place. Then the change in enthalpy can be calculated by

Equation 4.4. The value for specific heats for solids and liquids are available in literature [1,

Table A.3]3

2

The specific heat of liquid water at 25 C and 100kP a is 4.183kJ/kgK . It stays essentially constant except

close to the freezing (0 C) and boiling point (99.6 C) where it rises by less than one percent.

3

Often no distinction is made between Cp and Cv because the work performed when a solid or liquid is heated

at constant pressure is small because of the small change in the already small value of specific volume. Therefore

the additional heat that must be supplied to compensate for the work performed over and above the heat

necessary to increase the internal energy, will be negligible and their values will be essentially the same. Also it

is not common practice to heat a liquid at constant volume because of the high pressures generated because the

liquid cannot expand.

38

4.2

If the system boundaries are rigid and conditions inside the system boundaries are steady4 then

there will be no accumulation of mass or energy in the system. If the state and flow-rate of the

streams leaving and entering the system also does not change with time, then the rate at which

energy flows out of the system must be equal to the rate at which energy flows into the system.

This is true for many systems and the First Law can be written down after inspection. The rate

at which energy is entering the system is set equal to the rate at which energy is leaving the

system.

4.2.1

Shaft work

connecting the piston to a crankshaft as in an internal combustion engine, boundary work is used

to provide the energy necessary to rotate the crankshaft which in its turn turns the wheels of the

car or whatever load is connected to the engine. In the process boundary work is transformed

into shaft work. If this process takes place continuously, the shaft will rotate at a certain speed

under a certain torque, delivering mechanical power at a certain rate. This is called rate of shaft

work or power and the unit is [kW ]. In turbo machines, direct energy transfer between a fluid

and the blades attached to the shaft takes place.

Turbines convert the enthalpy of the incoming stream into shaft power. For compressible substances (gases), both internal energy and flow energy are converted into work and both temperature and pressure will decrease. For an incompressible substance no expansion takes place

and therefore the molecules cannot transfer their energy to a moving boundary and only flow

energy is converted into work and only the pressure will drop. Any change in the internal energy

is due to friction and turbulence in the turbine. In the case of gas and steam turbines, heat

loss is prevented as far as possible because energy lost as heat cannot be converted into work.

The rate of heat loss is therefore usually small in comparison to the rate at which energy enters

and leaves the system with the fluid and unless otherwise stated, turbines are assumed to be

adiabatic. Consider the turbine in Figure 4.2 below.

m

out

W

The only energy (in the form of internal energy plus flow energy) entering the system is the

4

The pressure inside a deflating tank will change with time and this is therefore an unsteady system.

39

enthalpy of the inlet stream. It enters the system at a certain mass flow rate m

in [kg/s].

Energy leaves the system as shaft work and also with the outlet stream - assuming an adiabatic

turbine. The first law states that the rate at which energy flows IN must equal the rate at which

energy flows OUT of the system. In mathematical terms:

out

mh

in = mh

out + W

The rate of energy transfer is [kg/s kJ/kg = kJ/s] or kW . The W stands for Watt. The rate

shaf t is called power and its unit is also [kW ]. The term work

of mechanical energy output W

is often used when talking about power. It is technically not correct but the true meaning is

usually clear from the context.

Example

Calculate the power delivered by the turbine shaft if the steam at the inlet of the turbine in

the figure above is at 1M P a and 500 C. The steam at the outlet is saturated vapor and at

5kP a. The flow-rate is 20kg/s.

Solution

The enthalpy of the steam entering the turbine is 3478.44kJ/kg . The enthalpy of the steam

at the outlet is 2561.45kJ/kg. Rearranging the energy balance:

out = m(h

W

in hout )

= 20(3478.44 2561.45)

= 18340kW

4.2.2

Heat

Heating and cooling are common and important processes. The equipment is designed in a

specific way as to maximize the rate of heat transfer. In the radiator of a car, fins are attached

to the outside of the water tubes to increase the heat transfer area in contact with air. An

important process in a power station is the generation of steam. Liquid water is fed to a boiler

and vaporized to produce steam. The only primary sources of heat are: combustion (usually

coal), nuclear radiation (usually the fission of uranium atoms), solar radiation or geothermal

heat. Consider the generic heater in the figure below.

Energy (as internal and flow energy) enters the system with the fluid flowing into the heater as

well as the heat supplied to the heater. This must equal the rate at which energy leaves the

system with the out-flowing fluid. In mathematical terms:

mh

in + Q in = mh

out

(4.5)

40

Example

Municipal water at 25 C and 300kP a is pumped through a solar water heater. The water

must be heated to 55 C. The solar water heater delivers heat at a rate of 1.2kW to the

water. At what rate must the water be circulated to ensure the stated outlet temperature?

A typical household geyser holds 150` water. How long will it take to heat up the geyser

from 25 C to 55 C?

Solution

Rearranging Equation 4.5 and getting the values for enthalpy from the saturated liquid

tables at the corresponding temperatures:

Q in

hin hout

1.2

=

230.2 104.87

kg

60s

= 0.0095747

s

min

kg

= 0.5745

min

m

=

The time necessary to heat up 150` of cold water (assuming 1kg = 1`):

t = 150kg

s

= 4.35h

0.0095747kg

Using Equation 4.4 and Cp = 4.183kJ/kgK results in h = 125.33kJ/kg while the values for

saturated liquid water (used in the calculation above) results in a value of 125.49kJ/kg.

The forms of energy considered are: enthalpy, heat, work, kinetic and potential energy. When

all are included the First Law for open systems becomes:(Assuming that heat is added to the

system and power delivered by the system.)

2

Q in +

V

gZin

m

hin + in +

2000 1000

out +

=W

V

gZout

m

hout + out +

2000

1000

For calculations with the First Law for open systems, the following relations are very useful. It

41

states that the volumetric flow rate is equal to the mass flow rate times the specific volume and

also to the flow velocity times the area of the pipe (perpendicular to the flow direction):

3

hm i

m

kg m3

q

= mv

=VA

m2

s

s kg

s

4.2.3

Kinetic energy

While the change in kinetic energy through a system is often low and therefore usually ignored,

there are instances where it is important. A rocket is propelled by the gases produced by the

combustion of the rocket fuel. The higher the velocity of the exhaust gases, the faster the rocket

will travel. In a rocket, a diverging nozzle is employed to convert as much as possible of the

enthalpy of the exhaust gases into kinetic energy to maximize the velocity of the rocket. In the

process the temperature and pressure of the exhaust gas drop. The ideal is that the pressure of

the exhaust gases at the exit of the nozzle is equal to ambient.

Example

Consider a rocket propelled by compressed air. The air at the inlet to the nozzle is at

700K and 500kP a and at the outlet of the nozzle the temperature dropped to 460K and

the pressure to 100kP a. Determine the velocity of the air at the outlet of the nozzle. It can

be assumed that the inlet velocity is negligible.

Solution

The heat loss will be very small compared to the rate at which energy flows through the

nozzle and therefore it is assumed that the nozzle is adiabatic. Letting m

= 1kg/s, an energy

balance over the nozzle gives:

2

hin = hout +

V out

2000

Getting the values for enthalpy from the table [1, Table A 7.1] enables us to calculate the

velocity at the outlet of the nozzle:

V out = (2000(713.56 462.34)) /2 = 708.9m/s

1

Under the assumption of ideal gas behaviour, pressures are irrelevant here. They are however

necessary to calculate the maximum possible outlet velocity by making use of the concept

of an ideal nozzle. The calculation of the maximum possible velocity will be done in later

chapters.

4.2.4

Potential energy

The change in potential energy is often much smaller than the change in the other terms in the

First Law and is often not taken into consideration. However if the change in elevation is large,

it must be taken into consideration:

42

Consider the Drakensberg pumped storage scheme. During times of low electricity demand,

water is pumped from the Kilburn dam (water surface 1256 m above sea level) to the Driekloof

dam (water surface 1702 m above sea level). During times of high demand, electricity can be

generated by reversing the flow direction of the water. The flow rate when generating electricity

is 312m3 /s. Assuming frictionless flow and zero turbulence, calculate the power output of the

turbine. Assume the water temperature in the Driekloof dam is 15 C and the ambient pressure

at the Kilburn dam is 100kP a.

The water at the dam surface is equal to the ambient pressure. Assuming a density of air of

1kg/m3 the ambient pressure at the surface of the Driekloof dam can be calculated as 95.6kP a.

Because there is no friction or turbulence, the internal energy will stay constant and because of

the small change in pressure and the small value of v, it is assumed that the enthalpy (h = u+P v)

also stays constant. Because the rate of heat loss (or gain) of the water will be much less than

the rate energy is passing through the pipe (mh)

assume that the change in kinetic energy is negligible.

The First Law now becomes:

out = mg

W

(Zin Zout ) = 1365M W

1000

4.2.5

Because open systems are so varied, it is usually the best practice to formulate the First Law

for each individual case. All the energy terms entering the system are written down and set

equal to all the energy terms leaving the system. In the examples below, kinetic and potential

energies are ignored. This may not be always valid.

Just as energy is conserved, mass is also conserved. If there are more than one inlet and/or

outlet stream, care must be taken to take all streams into account

a) Valves

Valves are used to control flow rate or reduce pressure. Valves do not perform work. The

rate at which energy flows through the valve mh

is much larger than any heat loss or gain

by the substance as it passes through the valve. Therefore a valve is usually assumed to be

adiabatic.

Therefore:

hin = hout

b) Compressors/pumps

43

A compressor is used to raise the pressure of a gas and a pump to raise the pressure of a

liquid. Both require power to accomplish this. Unless stated otherwise, compressors and

pumps are assumed to be adiabatic.

An energy balance gives:

in = mh

mh

in + W

out

c) Condenser

In a condenser, heat is removed and a vapor turned into a liquid. A condenser does not

perform or require power.

An energy balance gives:

mh

vapor = mh

liquid + Q out

d) Evaporator / Boiler

Liquid flows to an evaporator and is evaporated by the addition of heat as shown in Figure

4.3. Usually no specific measures are taken to superheat the vapor and the vapor and liquid

may be close to equilibrium. In power stations steam is produced in boilers from high pressure

liquid water. Usually the steam is also significantly super-heated before leaving the boiler.

An energy balance (from Figure 4.3) gives:

mh

liquid + Q in = mh

vapor

e) Heat exchanger

44

In a heat exchanger heat is transferred from a hot fluid to a colder fluid without the two fluids

mixing. An example is the radiator of a car where the water releases heat to the ambient air

and returns to the engine. The two fluids are separated by a conducting medium (usually

a metal). A schematic presentation of a counterflow heat exchanger is shown in Figure 4.7.

Also shown in Figure 4.7, is an often used symbol for a heat exchanger.

The system boundary is shown as a dotted line in Figure 4.7. Doing an energy balance over

the system boundary, results in the equation below. It is assumed that the rate at which heat

is exchanged between the two streams is much larger than possible heat exchange between

any (or both) of the streams and the environment and this exchange with the environment

is therefore ignored.

m

h hh |in + m

c hc |in = m

h hh |out + m

c hc |out

does not appear in the energy balance because it

Note that the rate of energy transfer (Q)

does not cross the system boundary.

4.3

In general, the First Law is used to calculate the amount of heat transferred during a process.

We will now consider a few special cases of heat transfer in single phase systems.

4.3.1

= 0) is

The rate at which energy must be supplied to heat a liquid in an open system (W

given by: Q in = m(h

out hin ). Often the pressure is unknown although it is known that the

water remains liquid. For instance, the inlet and outlet temperature of cooling water flowing

through a heat exchanger is often displayed by temperature gauges. In domestic applications,

only the temperatures of the different water streams flowing through a geyser or solar water

heater or a heat pump may be known. In such cases it can safely be assumed that the enthalpy

of the compressed liquid is independent of pressure as discussed in Paragraph 4.1.4. The change

in enthalpy is now given by dh = Cp dT . For liquid water Cp is not strongly dependent on

temperature and the heat transfer rate can be now be calculated by:

Q in = mC

p (Tout Tin )

45

(4.6)

If a solid or a liquid in an open container is heated at constant pressure (for instance a cup of

water) the heat transfer can be calculated by using the First Law for a closed system. Making

the same assumptions as above, this gives:

Qin = m((u2 u1 ) + P (v2 v1 ))

= m((u2 + P2 v2 ) (u1 P1 v1 )

= m(h2 h1 )

= mCp (T2 T1 )

The values of Cp are available in literature. See [1, Table A.3] for liquids and [1, Table A.4]

for solids. It is usually assumed that Cp = Cv . In the software program EES, no distinction

between Cp and Cv is made for solids and only C, the specific heat, can be selected.

The fact that work is ignored, also means that the type of process becomes irrelevant. Only

the change in internal energy is taken into consideration. Liquids and solids are usually not

heated under constant volume conditions because the pressure rises dramatically during heating

because of their low compressibility.

If in doubt about the validity of any of these assumptions, use the First Law.

4.3.2

Gases

For gases the volume will change and work in a closed system cannot be ignored. For a Perfect

Gas undergoing a constant pressure process, the heat transfer rate in an open system is given

by Equation 4.6 and for a closed system the equation derived in Paragraph 4.3.1 for liquids and

solids,

Qin = mCp (T2 T1 )

can be used. For constant volume processes in a closed system, Cv instead of Cp must be used.

For an Ideal Gas, compressed liquid or solid, if the value of the specific heat as function of

temperature is known, the value at the average temperature can be used.

4.4

Many important processes are not steady state. If a pressure vessel springs a major leak, it is

important to know how the temperature and pressure inside will change with time. Filling a

closed tank with a gas or a liquid is another example of unsteady state processes. A general

unsteady state process is shown in the figure below:

Unlike steady state processes, the amount of mass inside the system boundary does change with

time during an unsteady state process. Like energy, mass is also conserved and a mass balance

for the process in Figure 4.8 are:

46

m1 + min = m2 + mout

(4.7)

The summation signs are used to emphasize that more than one stream can flow into and more

than one stream can flow out of the system. Assuming a stationary system an energy balance

for an unsteady state process (in [kJ]) can be written as:

m1 u1 + (mh)in + Ein = m2 u2 + (mh)out + Eout

Where E accounts for all the other forms of energy (in [kJ]): heat, boundary and shaft work and

kinetic energy.

Example

Consider a rigid adiabatic tank. Initially the tank is completely empty m1 = 0. Air at 300K

now flows into the tank until the pressure rises to 400kP a. Calculate the final temperature.

Solution

No work is done and no heat is exchanged. Therefore the energy balance becomes:

min hin = m2 u2

From a mass balance it is clear that m2 = min and therefore u2 = hin . The enthalpy of air

at 300K is 300.47kJ/kg. The temperature of air with a specific internal energy of 300.47kJ/kg

is 419.2K

The flow energy of the air that flowed into the tank is converted into internal energy and

because of the rise in internal energy, the temperature also rises. Note also that the final

pressure does not have any influence on the final temperature.

Chapter 5

Reversible Systems

5.1

Consider a simple pendulum as shown in Figure 5.1 below. When the bobbin is released at

an elevated position, the bobbin accelerates in the gravitational field and potential energy is

converted into kinetic energy - as well as dissipated by friction at the pivot point, friction

between the air and the pendulum and also because of turbulence in the air caused by the

movement of the bobbin through the air.

At its lowest end the bobbins kinetic energy is at its maximum and its potential energy at its

minimum. Then the bobbin decelerates and kinetic energy is converted into potential energy

again until the bobbin reaches its highest elevation at the opposite end. The bobbin will swing

back and forth until all its energy has been dissipated by friction and turbulence and the bobbin

comes to a standstill at the lowest elevation. In order to keep the pendulum swinging, the

environment has to do work on the pendulum to overcome the effect of friction and turbulence

- like in a grandfather clock where the energy is supplied by a spring or weights. A frictionless

pendulum in an evacuated space can in principle keep on swinging forever. In such a (reversible)

pendulum, conversion between kinetic and potential energy takes place without any losses.

47

48

The two factors that make a pendulum irreversible are friction and turbulence which converts

the kinetic and potential energy into heat which cannot be - even in theory, be fully converted

back into potential or kinetic energy again. In the absence of these two factors the pendulum

would have been reversible. Unrestrained expansion is another factor that makes a process

irreversible. Consider a balloon that bursts. In order to restore the air that was inside the

balloon to its original condition, work is required (to compress the air) as well as heat exchange

with the environment (to lower the temperature after compression). The fact that outside action

is required to restore the system to its original condition means the process is irreversible. It is

possible (in principle) to expand air in a reversible manner. Consider an adiabatic frictionless

piston cylinder arrangement with compressed air inside. Initially the piston is restrained by

sand on top of the cylinder as shown in Figure 5.2 below:

Grains of sand are removed one by one, allowing the gas to expand slowly enough to ensure that

the pressure and temperature of the air inside stays uniform. The process can now be reversed

by placing the grains of sand back on the piston, compressing the gas slowly until the original

state has been reached.1

Consider energy conversion during this expansion process. In the expansion of the gas, work is

performed by the air molecules colliding with the piston, moving it upward. Some of the kinetic

energy of the colliding molecule is therefore converted into work and the kinetic energy of the

molecule is reduced. The total kinetic energy of the air molecules therefore drops. The internal

energy (and the temperature) of the gas will therefore also decrease. During the compression of

the gas, work is performed on the gas and the temperature will rise again to its original value.

The air inside a balloon that bursts in a vacuum (unrestrained expansion) does not perform work

- and assuming an adiabatic process, the internal energy of the gas remains constant. Assuming

air to be an ideal gas, the temperature of the gas will also remain constant. To compress the

gas again, work must be performed on the gas and its temperature will rise. To return the gas

to its original temperature, heat must be removed from the gas.

Heat transfer across a temperature difference is another factor that makes processes irreversible.

Consider a piston cylinder arrangement containing 1kg of saturated liquid water at 100 C. In

order for heat to be conducted across the walls of the container at a finite rate, heat at a slightly

higher temperature than 100C must be available. Let us assume a Thermal Energy Reservoir

1

It can be argued the effort from outside is necessary to remove and replace the grains of sand. If this

experiment was actually performed, it would have been a valid argument. But conducting this as a thought

experiment, no effort is required to remove the grains of sand, suspend them in the gravitational field and replace

them again. Even in a thought experiment, it is necessary to perform work when compressing the gas from the

balloon.

49

5.2. ENTROPY

(TER)2 at 110 C supplies the heat and the water boils at constant pressure until a saturated

vapor results as shown in Figure 5.3 below.

In order to reverse the process a TER at a lower temperature than 100 C must be available to

act as a heat sink. Lets assume heat is rejected to a TER at 90 C. The vapor condenses at

constant pressure and a saturated liquid at 100 C results again - so the water inside the piston

cylinder is restored to its original condition, but the environment has changed. The temperature

of the 2258kJ of heat necessary to vaporize the water, has changed from 110 C to 90 C. In

a reversible process there will be no temperature gradient and the heat will be absorbed and

rejected at the same temperature - making it possible to reverse the process without changing

the temperature of the heat.

Although not relevant in processes considered here, mixing of two dissimilar substances is also

irreversible. Once the coffee granules have dissolved in the water, the water and coffee granules

cannot be restored to its original condition without considerable effort. We have considered four

factors that make processes irreversible:

Friction and turbulence

Unrestrained expansion

Heat transfer over a finite temperature gradient

Mixing of dissimilar substances

In order to quantify the degree of (ir)reversibility, a new property, entropy is defined.

5.2

Entropy

disorder can be described in terms of position and in terms of velocity. For instance, particles

at rest can be ordered or disordered. Also, particles moving at different velocities and directions

are more disordered than particles all moving at the same velocity and direction. In the gas

phase, the molecules move about at random, collide and change direction. Therefore the entropy

2

A TER is a body with an infinitely large heat capacity (and constant volume) and can therefore supply and

receive heat without its temperature changing. Because its volume stays constant, the TER also does not perform

any work.

50

of a substance should be higher in the gas phase and lower in the solid or liquid phase. Also,

according to the kinetic gas model, the higher the internal energy of a gas, the higher the kinetic

energy of the gas molecules. Therefore entropy should rise as heat is added to a gas, when a

solid melts or a liquid boils to form a vapour. This leads to the first very important statement3

about entropy:

Entropy transfer accompanies heat transfer. In a reversible system this enables us to

calculate the change in entropy using the definition of entropy:

dS =

Q

T

(5.1)

reversible

where Q is the differential amount of heat exchanged in a reversible process and T the temperature of the system boundary. In a reversible system there will be no temperature gradients in

the system.

To illustrate how the flow of heat leads to a change in entropy, consider 1kg of saturated liquid

water at 100kPa in a closed system. The water is heated at constant pressure (and therefore

also at constant temperature) until it is a saturated vapor. The heat necessary to vaporize the

water is 2 258kJ as calculated from the First Law. Because the temperature remains constant

during the process, the equation above is easily integrated to give the change in entropy for the

water upon evaporation:

S =

Qin

2258

kJ

=

= 6.057

T

99.63 + 273.15

K

If the water is condensed again and the heat released at the equilibrium temperature, the

system is back at its original condition and the heat is still at the same temperature it has

been supplied to the system. In this case the evaporation and condensation were done infinitely

slowly in order to make sure that the vapor and liquid were at the same temperature and there

were no temperature gradients.

Lets consider a process where the temperature changes. A perfect gas is heated at constant

pressure from T1 to T2 The heat required is given by:

Q = Cp dT

replacing Q in the definition of entropy and integrating gives:

s = Cp

T2

T1

dT

T1

= Cp `n

T

T2

(5.2)

It is possible, working from a suitable reference point, to calculate the value of entropy at any

state. It can be shown that the value of entropy so calculated is independent of the calculation

path and depends only on the reference state and the end state. This is a necessary and sufficient

condition to make the following statement:

3

In this chapter we will encounter a few of these statements about the nature of entropy

51

Entropy is a property Entropy can therefore be used in the specification of the state of a

substance. For a single phase substance, if the value of two independent properties are fixed,

the state is fixed. Entropy cannot be measured but can only be calculated. It is therefore an

abstract property - like the momentum of a particle.

5.3

Determination of Entropy

We distinguish between three types of substance: Real and condensible substances, Ideal gases

and Perfect gases (Ideal gases with a specific heat independent of temperature). As with other

properties a distinction is made between specific entropy - the entropy per kilogram of substance,

using the lowercase s with units of [kJ/kg K] and total entropy using uppercase S with units

of [kJ/K].

5.3.1

Ideal gases

An equation giving the change in the entropy of an ideal gas can be derived using the differential

form of the First Law for a closed system. Consider a unit mass:

q = du + w

For a reversible process w = P dv and for an ideal gas, P = RT

v and du = Cv dT . Using these

equations and the definition of entropy to replace the appropriate terms in the First Law, the

following equation results:

T ds = Cv dT + RT

dv

v

s2 s1 =

T2

Cv dT + R `n

T1

v1

v2

(5.3)

Using the Ideal Gas Law v = RT /P to get rid of the volume terms in the equation above and

remembering that Cp = Cv + R and rearranging, the following equation results:

s2 s1 =

T2

T1

Cp

dT

P2

R `n

T

P1

(5.4)

Equation 5.4 is similar to Equation 5.2 but with a term to account for change in pressure. In

general the specific heat Cp is not a simple function of temperature and in order to prevent

having to do the integration every time a value for entropy is required, the entropy of different

ideal gases as function of temperature, at 100kP a, relative to some reference point has been

calculated and tabulated. To find the entropy at a pressure other than 100kP a the equation

above is rewritten to only give the change in entropy with pressure:

52

sT ,P = soT R `n

P

100

(5.5)

Where sT ,P is the entropy at the specified temperature and pressure and soT is the entropy at

the specified temperature but at 100kP a. Its value can be found in tables giving the properties

of gases under the assumption of ideal gas behaviour.

Example

Calculate the entropy of air at 200kP a and 25 C

Solution

s200kP a;25C = so298.15K Rair `n

= 6.863 0.287`n

P

100

200

= 6.664kJ/kg K

100

The answer seems logical as one can expect the molecular disorder to decrease as the pressure

increases.

Because entropy is a property it can be used to define the state of the air. Because air is a single

phase substance the value of two independent properties must be specified to fix the state.

For specified values for entropy and temperature, the pressure can be determined directly from

Equation 5.5 but for specified values for entropy and pressure, an iterative procedure may be

necessary to determine temperature from the tabulated values4 . Once the values of temperature

and pressure are known, the Ideal Gas Law can be used to calculate the specific volume.

5.3.2

Perfect gases

For the mono-atomic (ideal) gases (Ar, Ne, He, Kr, Zn) Cp is virtually independent of temperature and collectively they are called perfect gases. For a Cp 5 independent of temperature

Equation 5.4 is easily integrated to give the change of entropy with temperature and pressure:

s2 s1 = Cp `n

T2

P2

R `n

T1

P1

The change of entropy with temperature and specific volume is obtained by integrating Equation

5.3

s2 s1 = Cv `n

4

T2

v2

+ R `n

T1

v1

Use the values in the example above to illustrate this for yourself

Tables giving the properties of gases usually give the values at a specific temperature. Under the assumption

of a constant specific heat this value can be used at any temperature.

5

53

In this case, because it is only possible to calculate the change in entropy, it is not possible to

use entropy as one of the variables that define the state. The same is true for internal energy

and enthalpy - because, for a perfect gas, only the change in u and h can be calculated. A

combination of two other variables (P, T, v) must be used to fix the state.

5.3.3

Values for entropy are tabulated in the steam tables for saturated water (as a function of pressure

or temperature) and for super-heated water (as a function of pressure and temperature). Note

also that the entropy of saturated liquid water at the triple point (0.01C and 0.6113kPa) is

(arbitrarily) chosen as zero.

For a single phase substance, once the values of two independent properties are specified, the

state is fixed while for a two phase mixture, temperature and pressure are no longer independent

and only one of the two can be specified. For a specific set of variables, it is therefore important

to first determine the phase.

Example

Calculate the temperature and enthalpy of steam at 10kP a with an entropy of 7kJ/kg K

Solution

The value for entropy is larger than the value for entropy for the saturated liquid at this

pressure (0.6493kJ/kg K) but smaller than the value for the saturated vapor (8.1502kJ/kg

K) This means that it is a two phase liquid and the temperature is the equilibrium value at

10kP a, 45.81C. To determine the enthalpy of the two phase mixture (TPM), the quality

must be known. This is calculated from the value of the entropy:

sT P M = sg x + sf (1 x)

7 = 8.1501x + 0.6492(1 x)

x = 0.8467

hT P M = 0.8467 2584.63 + (1 0.8467)191.81 = 2217.7kJ/kg

According to the steam tables, the entropy of saturated liquid water at 100kPa is

1.3026kJ/kg K and of saturated water vapor, 7.3594kJ/kg K. The change in entropy

upon vaporisation is therefore 6.0568kJ/kg K. This is the same as the value calculated

from the definition of entropy.

5.4

From the definition of entropy, it is clear that the entropy during an adiabatic reversible process

will stay constant. During the adiabatic reversible expansion of a gas in a piston/cylinder setup,

54

work is performed but the entropy does not change. This means that work is free of entropy.

This is also the case for open systems. As steam flows through an adiabatic reversible turbine,

the entropy of the steam does not change (the entropy at the inlet and the outlet will be the

same) although the turbine delivers power. From this follows the third very important statement

about entropy:

There is no entropy transfer associated with energy transfer as work or power. This

is in contrast to heat, where heat transfer leads to a change in entropy - as is evident from the

definition of entropy in Equation 5.1.

5.5

Reversible processes

Because no heat transfer takes place, the entropy during an adiabatic reversible process does

not change. Now consider heat exchange between a system and a heat source. For this process

to be reversible, the system and the heat source must be at the same temperature. From the

definition of entropy, it is clear that the increase in the entropy of the system will be the same

as the decrease in the entropy of the heat source and this leads to the fourth very important

statement about entropy:

For reversible processes, the total entropy (Stotal = Ssystem +ST ER ) remains constant6 .

This means that for a reversible process, we can do an entropy balance. This principle will now

be demonstrated for the following reversible processes:

Closed and open adiabatic systems

Closed and open systems with heat transfer

Heat engines and heat pumps - a special type of closed system.

5.5.1

Closed systems

Consider the reversible adiabatic compression of a gas

55

Because no heat flow has taken place and because there is no entropy transfer associated with

work, it follows from the definition of entropy Equation 5.1 that S2 = S1

Example

Calculate the work required to compress 1kg of Helium at 300K adiabatically and reversibly

from 100kP a to 200kP a

Solution

The entropy will stay constant during this process and assuming Helium to be a perfect gas:

s2 s1 = Cp `n

T2

P2

R `n

=0

T1

P1

T2 is now the only unknown and its value can be calculated from the equation above as

359.6K and work from the First Law (Q = 0):

Win = m(u2 u1 ) = m Cv (T2 T1 ) = 3.1156(359.6 300) = 185.7kJ

Open systems

For an adiabatic, steady, open system it means that the rate at which entropy is entering the

system with mass flow will be the same as the rate at which it is leaving the system with mass

flow. For a system with only one inlet and one outlet:

ms

i = ms

u

Example

Steam at 400C and 400kP a flows to a reversible adiabatic turbine at a rate of 1kg/s. The

pressure at the outlet is 100kP a. Calculate the power delivered.

Solution

An energy balance for the turbine gives:

out

mh

in = mh

out + W

Because this is an adiabatic reversible turbine, the entropy at the outlet will be the same

as the entropy at the inlet (sin = 7.8984 kJ/kgK ). We therefore know the the value of two

variables at the outlet, fixing the state. At a pressure of Pout = 100kP a and an entropy

of sout = 7.8984 kJ/kgK the enthalpy of steam is 2906 kJ/kg and the power delivered by the

turbine:

out = m(h

W

in hout ) = 3273 2906 = 367kW

56

Ignoring potential and kinetic changes and replacing enthalpy (h) with u + P v, the First Law

for an adiabatic pump becomes:

in + uin + Pin vin = uout + Pout vout

W

In a reversible pump there will be no friction, turbulence or unrestrained expansion and the

internal energy will not change. Assuming a constant specific volume:

in = v(Pout Pin )

W

A more rigorous derivation can be found in Thermodynamics by S Klein and G Nellis [3, p. 404]

5.5.2

Heat is usually supplied by a heat source or rejected to a heat sink (often the environment).

If we can assume assume a uniform temperature inside the source or sink and an infinite heat

capacity its temperature will not change and we call it a Thermal Energy Reservoir (TER). For

a TER we also assume a constant volume (so no work is performed). The change in entropy of

a TER can be calculated using the definition of entropy.

Example

Assume that the environment is a heat sink at 25 C. Calculate the change in the total

entropy of the environment with the addition of 20M J of heat.

Solution

From the definition of entropy:

dS =

Senvironemnt =

Q

T

reversible

20 000

= 67kJ/K

25 + 273.15

Closed systems

When the system release (absorbs) heat its entropy will decrease (increase) but the entropy of

the TER receiving (supplying) the heat will increase (decrease) by the same amount because

the total entropy must stay constant.

57

Example

One kilogram of steam at 200kP a and 400 C is expanded at constant temperature to

200kP a in a piston cylinder arrangement exchanging heat with a TER at the same

temperature. Determine the work without making any assumptions.

Solution

R

The equation W = P dV can be integrated numerically but that would not be an exact

solution. So another strategy must be devised. The First Law for closed systems:

Qin = m(u2 u1 ) + Wout

The initial and final temperatures and pressures are known, so the u1 and u2 can be read

from the steam tables. The amount of heat exchanged is calculated from an entropy balance.

The change in the entropy of the steam is equal to the change in the entropy of the TER

supplying the heat:

QT ER,out

m(s2 s1 ) =

TT ER

Entropy can be read from the steam tables and QT ER calculated:

QT ER,out = (8.5434 8.2217) (400 + 273.15) = 216.55kJ

QT ER,out is equal to Qsteam,in . The First Law therefore gives:

Wout = 216.55 (2967.85 2966.69) = 215.39kJ

of work done by the system on the environment. It is important to note the sign of Q. The

formulation of the First Law used here is valid for heat supplied to the system while work

is performed by the system. In this case the heat was supplied to the system and the heat

term in the First Law are positive. Had heat been released by the system, the heat term in

the First Law would have been negative.

Open systems

For an open system it means that the rate of change of the entropy of the TER must be equal

to the rate of change on the entropy of the substance. For a process where heat is supplied by

the TER:

Q T ER,out

= ms

out ms

in

TT ER

58

Example

Air at 300K and 100kPa is compressed at constant temperature to 200kPa in an reversible

compressor at a rate of 2kg/s exchanging heat with a TER at the same temperature.

Determine the power required.

Solution

During compression, the temperature of the air will rise. In order to maintain a constant

temperature, heat must be released. An enthalpy balance gives:

in = mh

mh

in + W

out + Q out

Assuming air to be an ideal gas, enthalpy is not dependent on pressure and hin = hout . This

means that the power required is the same as the heat transfer rate. In order to calculate

the heat transfer rate an entropy balance is performed. Because this is a reversible process,

the total entropy stays constant and the rate at which the entropy of the air decreases must

be the same as the rate at which the entropy of the TER increases:

m(s

in sout ) =

Q T ER,in

TT ER

For air:

sin sout = m(s

o300K (so300K Rair `n

200

))

100

Q = 300 2 0.287`n 2 = 119kW

and:

5.5.3

out = Q = 119kW

W

A heat engine is used to convert heat into (shaft) work. Heat engines form the basis of electricity

generation where they are used to convert the heat released by the burning of coal or fissile

nuclear material or solar energy to shaft work to turn an electric generator and also in automobile

engines where the heat released by the combustion of gasoline is converted to the work necessary

to turn the wheels of the car.

Consider a reversible heat engine called the Carnot cycle. Saturated water at high pressure

and temperature enters a boiler and leaves the boiler as saturated vapor at the same pressure.

The saturated vapor enters an adiabatic reversible turbine and shaft work is produced. The

two-phase mixture that leaves the turbine is almost completely condensed at constant pressure

and temperature and enters an adiabatic reversible pump with an outlet pressure equal to the

inlet pressure of the boiler. This saturated liquid enters the boiler to complete the cycle. The

59

components and flow direction of the Carnot heat engine is shown in Figure 5.4 below. The

high temperature TER supplies heat at the evaporating temperature and steam condenses at

the same temperature as that of the low temperature TER.

A coal-fired power plant (and most nuclear plants) contains a somewhat similar heat engine.

The burning of coal (or fission of uranium atoms) supplies high temperature heat to the heat

engine and low temperature heat is rejected to the environment.

If we take the reversible heat engine as a black box with high temperature heat entering and

power and low temperature heat leaving as shown in Figure 5.5, entropy can be used to calculate

the maximum rate that power can be produced from high temperature heat.

Because all the processes involved are reversible the total entropy will be constant and therefore

the rate at which the entropy of the high temperature TER decreases, will be the same as the

rate at which the entropy of the low temperature TER increases. No mass flow is taking place

across the boundaries of the heat engine.

Q H

Q L

=

TH

TL

The first law states that the energy must be conserved. The pump will consume a little of the

energy produced by the turbine. Therefore the net work is the work delivered by the turbine

minus the work consumed by the pump. For the heat engine an energy balance gives:

60

nett + Q L

Q H = W

Because a heat engine usually rejects its heat to the environment, and this heat is of no value,

while QH costs money to generate, QL is usually eliminated from the two equations above to

give the reversible power for a heat engine:

nett = Q H

W

TL

1

TH

Example

A reversible heat engine receives heat at a rate of 10kW from a high temperature reservoir

at 1000K and rejects heat to the environment at 25 C. Calculate the power delivered.

Solution

25 + 273.15

Wnett = 10 1

1000

nett = 7kW

W

This is quite high. In actual fact, a coal power station typically converts a third of the energy

in the coal into electricity.

This cycle can be reversed to give a heat pump - a device that pumps heat against the

temperature gradient from a low temperature to a higher temperature. This principle can be

used to extract heat from the environment, raise its temperature and use this high temperature

heat to heat domestic water.

Example

A typical domestic hot water cylinder contains 200kg of water. Calculate the heat necessary

to raise the temperature from 15 C to 60 C using an electrical resistance heater and a

reversible heat pump extracting heat from the environment at 15 C.

Solution

Assuming a specific heat of 4.184kJ/kg K for water the heat necessary is:

Q = mCp (T2 T1 ) = 200 4.184(60 15) = 37 656kJ

This heat has to be supplied by the resistance heater. A reversible heat pump will require

(It is left to the reader to show that this equation is also valid for heat pumps):

Wnett

288.15

TL

= QH 1

= 37 656 1

= 5 086kJ

TH

333.15

61

The heat pump therefore requires only 13.5% of the energy required by the resistance heater.

The running cost will be lower but additional capital outlay will be necessary. Heat pumps will

therefore be at their most economical where there is a constant consumption of hot water - so

the saving in running cost can cover the capital expenditure associated with the purchase of the

heat pump.

A refrigerator also uses this principle to pump heat from the inside of the refrigerator (at a low

temperature) to the environment at a higher temperature.

5.6

Enthalpy revisited

Enthalpy is defined as the sum of internal energy (u) and what is often called flow energy

(P v) which is often difficult to conceptualize. The application of the First Law on open, steady

state, reversible processes, gives another view of enthalpy that may make the concept of flow

energy easier to grasp. Consider water flowing in an adiabatic pipe. Also replace enthalpy (h)

with u + P v or rather u + P :

ui +

V 2i

gZi

Pe

Ve2

gZe

Pi

+

+

= ue +

+

+

i

2000 1000

e

2000 1000

The four types of energy represented here are: u: internal energy, P : flow energy, 12 V 2 : kinetic

energy and gZi : potential energy. If there is friction or turbulence, some of the flow, kinetic or

potential energy will be converted into internal energy. In a reversible system there is no friction

and the internal energy will not change and the First Law above reduces to:

Pi

Vi2

gZi

Pe

Ve2

gZe

+

+

=

+

+

i

2000 1000

e

2000 1000

This is also known as the Bernoulli equation and its units are [kJ/kg]

Example

A man uses a hose pipe to wash debris from the gutters of his house. The exit of the hose

pipe is 3m higher than the inlet of the hose pipe at the tap. Due to a nozzle at the end of

the hose pipe the water is accelerated from 5m/s at the inlet to an unknown value at the

outlet. The municipal pressure of the water at the tap is 300kP a and the ambient pressure

85kP a. Assuming a constant density of 998kg/m3 for the water and reversible (frictionless)

flow, calculate the velocity at the outlet of the nozzle.

Solution

From the Bernoulli equation:

300

52

85

V2

9.81 3

+

=

+

+

998 2000

998 2000

1000

62

Therefore:

Vout = 19.92m/s

Because the specific volume of the water stays constant, the change in flow energy is directly

proportional to the change in pressure. As the pressure drops (flow energy decreases) the

water is accelerated (kinetic energy increases) and the elevation increased (potential energy

increases).

Assuming a very long thin adiabatic hose pipe with high friction (with no change in kinetic

and potential energy) all the flow energy will be converted into internal energy. From the

First Law the rise in the temperature of the water can be calculated:

Pin Pout

= u = Cv T

(300 85)

= 0.052C

4.184 998

This is a small change in temperature and is usually ignored.

T =

Because the change in pressure for incompressible substances is directly proportional to the

change in flow energy, the perception develops that (P v), flow energy (pressure) is the main

source of energy, also for compressible substances. This is not correct. Consider the Helium

turbine in Paragraph 5.5.1

The internal energy changes by:

u = Cv (Tin Tout ) = 3.11 (700 461.8) = 742.23kJ/kg

while the flow energy (P v = RT ) changes by:

P v = R(Tin Tout ) = 2.077 (700 461.8) = 494.74kJ/kg

The total is the same as in the example: 1237kJ/kg. The internal energy supplies the bulk

of the power. For substances whose volume is not that dependent on pressure - in the case of

gases, those with a smaller value of R - the fraction of the power supplied by flow energy will

be even smaller. A turbine running on air at the same inlet temperature and between the same

pressure limits, will deliver 191kJ/kg with only 52kJ/kg supplied by flow energy.

In the case of a turbine powered by liquid water, the internal energy will change very little and

the power is completely due to the change in flow energy. Internal energy changes only due to

irreversibility.

Chapter 6

Real Systems

Real systems are characterized by friction, turbulence, unrestrained expansion, temperature

gradients and mixing of dissimilar substances and are therefore irreversible. Molecular disorder

increases and the total entropy is no longer constant but is constantly increasing.

6.1

A few numerical examples will now be done to illustrate how entropy is generated in real systems.

6.1.1

Friction

In thermal fluid systems friction is generally between the fluid and the containing surface. Turbulence will cause friction between fluid molecules.

Example

In an refrigerator, saturated liquid freon flows through a thin capillary tube. Due to fluid

friction the pressure drops and because of the drop in pressure, the liquid boils and a two

phase liquid results. Because this is an adiabatic process, the enthalpy stays constant and

because a vapor has a higher enthalpy than a liquid, the temperature of the resulting two

phase mixture must be lower than the temperature of the initial saturated liquid. (The

liquid must sacrifice some of its internal energy to provide the energy to form a vapor.)

Calculate the entropy before and after the capillary tube. Assume the freon at the inlet is

saturated R134 liquid at 35 C and the pressure downstream is 100kP a

Solution

For an adiabatic capillary tube:

hin = 100.9kJ/kg = hout

63

64

From the pressure and enthalpy at the outlet the rest of the variables can be calculated:

T = 26.4 C and x = 0.385. The entropy increased from 0.3714kJ/kgK to 0.4106kJ/kgK

It is clear that the entropy increased and that entropy has therefore been created. The cause

of this increase is friction in the capillary tube.

6.1.2

Unrestrained expansion

When gas is expanded in a piston/cylinder arrangement, the molecules of the gas is restrained

by the piston. The molecules collide with the moving piston, transferring their energy to the

piston. In a reversible process no pressure gradient in the gas exists. If the rate of expansion

is increased, a pressure gradient may develop and the pressure at the moving boundary may be

lower. Then the amount of work performed by the system decreases. (W = P V ) The faster

the expansion takes place, the more unrestrained it becomes, the bigger the pressure gradient

becomes and the lower the amount of work performed.

Example

Consider a balloon, containing 1kg of air at 100kP a and 25 C bursting in an evacuated

adiabatic container. The final pressure in the container is 10kP a. Calculate the change in

the entropy of the air.

Solution

Because the process is taking place in a vacuum, the pressure at the boundary of the expanding gas is zero. No work is therefore performed. Because no heat transfer takes place

the internal energy stays constant. For an ideal gas the internal energy is not dependent on

pressure and therefore the temperature of the gas does not change. The change in entropy

is therefore given by:

s2 s1 = R`n

10

kJ

P2

= 0.287`n

= 0.66

P1

100

K

It is clear the the entropy at the end of the process is more than at the beginning and

because this is an adiabatic process, that entropy has been created.

If a balloon bursts in the earths atmosphere, the pressure at the boundary of the expanding

gas is equal to the ambient pressure and some work is necessary to push away the atmosphere

therefore some work will be performed and the temperature of the gas will drop. However

this is still not a reversible process and a pressure gradient will exist causing the loud sound

when a balloon bursts.

6.1.3

A temperature difference is necessary to provide the driving force for heat transfer. In reversible

systems we assumed an infinitely small temperature difference leading to an infinitely slow rate

65

of heat transfer. In real systems a finite temperature is necessary to make a finite rate of heat

transfer possible.

Example

Consider a system consisting of two TERs. The one at 400K and the other at 300K. 100kJ

of heat is transferred between them. Calculate the change in entropy of the system.

Solution

The heat will flow from the 400K TER to the 300K TER. The entropy of the 400K TER

will decrease:

100

kJ

S400K =

= 0.25

400

K

The entropy of the 300K TER will increase:

S300K =

kJ

100

= 0.33

300

K

In principle it is possible to install a heat engine between the two TERs above and generate

work from the 100kJ of heat released by the high temperature TER. A reversible heat engine

will generate no entropy. In the irreversible process above the ability of the high temperature

heat to do work was destroyed and in the process, entropy was generated.

6.2

In the previous chapter entropy was considered from a statistical viewpoint. (Entropy is a

measure of molecular disorder.) Entropy can also be defined as: Entropy gives an indication

of the unavailability of heat, internal energy and enthalpy to perform work. It is

clear from the examples in Paragraph 6.1 that the generation of entropy is associated with a

reduced work output.

Example

Consider two piston cylinder arrangements containing 1kg of Helium at 25 C The Helium

in the first cylinder is at atmospheric pressure (85kP a) and the other at 170kP a. Calculate

the difference in entropy between the two. Calculate the work performed if both of them

are expanded isentropically to the ambient pressure of 85kP a

Solution

As the temperatures are the same, the difference in entropy is given by:

s85kP a s170kP a = 0.287`n

85

kJ

= 0.199

170

kg K

66

The entropy of the Helium at 170kP a is the lower of the two. The Helium at ambient

pressure cannot do any work. For the calculation of work done in the expansion of the

Helium at 170kP a, the First Law can be used. But first the temperature after expansion to

85kP a has taken place has to be calculated:

T2 = T1

P2

P1

k1

k

85

= 298.15

170

1.6671

1.667

= 225.9K

Wout = m Cv (T1 T2 ) = 3.116(298.15 225.9) = 225kJ

It is clear that the Helium at the higher pressure can perform more work than the Helium

at the lower pressure. Also the Helium at the higher pressure has the lower entropy. This

illustrates the fact the entropy is an indication of the unavailability of internal energy to do

work.

This has implications for the efficiency of converting internal energy, enthalpy and heat into

work. As entropy is generated in real systems, the ability of the internal energy, enthalpy and

heat to perform work, will decrease. The generation of entropy should therefore be minimized

if work output is to be maximized.

6.3

In order to determine where entropy is generated in the system, the flow and generation of

entropy in the system must be studied:

As all the energy in boundary and shaft work as well as kinetic and potential energy is

available to perform work, they are free of entropy. As stated before: There is no entropy

transfer associated with the transfer of energy as work or power.

Entropy is also a property. Therefore the rate of entropy transfer associated with mass

transfer in an open system is equal to ms[

kJ/Ks]. The entropy associated with the mass

in a closed system is equal to ms[kJ/K ].

In any real process, entropy is generated (S gen > 0) in open systems and (Sgen > 0) in

closed systems . In a reversible process the total entropy stays constant (Sgen = 0 or

S gen = 0)

Entropy transfer is also associated with heat transfer. The entropy transferred with heat

is determined by the temperature of the heat where it crosses the system boundary.

The transfer of entropy with heat transfer will now be considered in more detail:

67

6.3.1

The fact that entropy transfer accompanies heat transfer, follows from the definition of entropy

and the definition of entropy enabled us to calculate the change in entropy of a TER exchanging

S =

Q

TT ER

S is the rate at which the entropy of the TER is changing and it can therefore be seen as a

stream of entropy that flows out of or into a TER. Consider two TERs at different temperatures, say 400K and 300K, connected by a conducting material. The conducting material is the

system (the upright rectangle shown in Figure 6.1). The temperature of the system boundary

is the same as that of the TER where the TER and the system is in contact. At a heat transfer

rate of 100kJ/s from the TER at 400K, entropy flows at a rate of 100/400 = 0.25kJ/s K from

the TER. As energy is conserved, the rate of heat transfer into the TER at 300K will be the

same as the rate out of the TER at 400K - 100kJ/s but the rate at which entropy flows into the

K. This means that entropy is being generated in the

The generation of entropy can take place inside and/or outside the system. Sometimes it may

be advantageous to manipulate the location of the system boundary to place the cause of irreversibility either inside the system or outside in the environment. This can result in one of

two types of system.

6.3.2

By locating all irreversibilities outside the system boundary, an internally reversible system

results. The principles of reversible processes (Sgen = 0) can now be applied on the system by

using the concept of entropy transfer. This sometimes make it possible to solve problems that

could not be solved otherwise.

Example

One kilogram steam in a piston cylinder arrangement at 300kP a and 200 C is compressed at

constant temperature to a pressure of 400kP a, releasing heat to the environment. Calculate

the work required analytically.

68

Solution

Because there is not a simple relationship between the pressure, volume and temperature

for steam, work has previously been determined numerically (Paragraph 2.2.2). However,

the First Law contains a work term and can be used if the amount of heat exchanged can

be determined. The heat exchange takes place over the temperature difference between the

steam and the environment and this is an irreversible process and entropy is generated.

The entropy generated can only be calculated if the amount of heat transferred is known

and that is what we want to determine! So we are stuck. But by defining the steam

as the system, an internally reversible process results and the entropy transfer across the

system boundary can be calculated because the temperature of the boundary is uniform

and constant. The irreversibility is located outside the system and does not influence the

calculations. An entropy balance can be done for the steam. The change in entropy of

the steam is equal to the transfer of entropy because it is an (internally) reversible process.

m(s1 s2 ) =

Qout

Tsystem boundary

Qout = Tboundary m(s1 s2 ) = (200 + 273.15)(8.1579 7.1706) = 467.14kJ

From the First Law (heat is released therefore the negative sign):

Win = m(u2 u1 ) +1 Q2 = (2659.85 2646.83) 467.14 = 454.12kJ

The work is negative. This means work was required to compress the steam, which makes

sense. Note that the internal energy changed due to the change in pressure because steam

is not an ideal gas. For an ideal gas the heat exchange would have been equal to the work.

6.3.3

Because entropy generation impacts negatively on the efficiency of energy conversion into work,

it may be necessary to include the irreversibility in the system to quantify its efficiency. In the

case of turbines and compressors the irreversibility is necessarily part of the system and must be

taken into consideration. The efficiency of internally irreversible systems are often determined

by comparing their real performance to the performance of a reversible system.

Turbines

The actual power delivered by turbine divided by the power a reversible turbine (with the same

outlet pressure) would have delivered:

turbine =

actual

W

isentropic

W

69

is called the isentropic efficiency.

Example

Suppose the steam turbine on page 55 is not isentropic but has an isentropic efficiency of

90% Calculate the power delivery and outlet temperature of the actual turbine.

Solution

The isentropic power the turbine delivers is 367.3kW . The actual power is therefore:

actual = 0.9 367.3 = 330.6kW

W

As a smaller fraction of the energy in the steam has been converted into power, the outlet

temperature of actual turbine will be higher than that of the isentropic turbine. An energy

balance for the actual turbine:

actual + mh

mh

in = W

out,actual

gives a value of 2943kJ/kg for the actual outlet enthalpy that corresponds to 234.3C for

Tout,actual which is higher than the isentropic outlet temperature of 215.8C

Compressors

The power required by an isentropic compressor will be lower than the power required by a real

compressor because of turbulence and friction in the real compressor. Therefore the efficiency

for compressors is given by:

compressor =

isentropic

W

actual

W

Example

Saturated steam at 100kP a flows at a rate of 1kg/s to a compressor with an adiabatic

efficiency of 80%. The pressure at the outlet of the compressor is 200kP a. Calculate power

required by the turbine and the outlet temperature.

Solution

isentropic

W

The power required is given by the efficiency: compressor = W

actual The isentropic power

required, is given by an enthalpy balance:

mh

in + Wisentropic = mh

out,isentropic

The outlet enthalpy of the isentropic turbine is found by interpolation at 200kP a and an

entropy of 7.3593kJ/kg K to be 2803kJ/kg. This gives isentropic power required:

isentropic = 2803 2675 = 128kW

W

70

actual = 128/0.8 = 160kW

W

The actual outlet temperature can be found by doing an enthalpy balance over the actual

compressor:

mh

in + Wactual = mh

actual

This gives an outlet enthalpy for the actual compressor of 2835kJ/kg. The temperature of

steam at this entalpy and 200kP a, is 182.7C

Bibliography

[1] Borgnakke C and Sonntag RE. Fundamentals of thermodynamics, 7th ed. Wiley.

[2] Cengel YA and Boles MA. Thermodynamics: An engineering approach, 4th ed. McGraw-Hill.

[3] Klein S and Nelles G Thermodynamics Cambridge University Press

71

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