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Read BS, Chapter 2

2.1 Thermodynamic system and control volume

We take the following denitions:

Thermodynamic system: a quantity of xed mass under investigation,

Surroundings: everything external to the system,

System boundary: interface separating system and surroundings, and

Universe: combination of system and surroundings.

The system, surroundings, system-boundary for a universe are shown for a potato-shaped

system in Fig. 2.1. We allow two important interactions between the system and its sur-

roundings:

heat can cross into the system (our potato can get hot), and

work can cross out of the system (our potato can expand).

Now, the system boundaries can change, for example the potato might expand on heating,

but we can still distinguish the system and the surroundings. We now dene an

isolated system: a system which is not inuenced by its surroundings.

Note that a potato with thick and inelastic skin will be isolated. We distinguish the system,

which has constant mass, but possible variable volume, from the

Control Volume: xed volume over which mass can pass in and out of its boundary.

The control volume is bounded by the

29

30 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

system

surroundings

system boundary

heat in

work out

universe

Figure 2.1: Sketch of a universe composed of a system, its surroundings, and the system

boundary.

Control Surface: boundary of the control volume.

The mass within a control volume may or may not be constant. If there is uid ow in

and out there may or may not be accumulation of mass within the control volume. We will

mainly study cases in which there is no accumulation, but this need not be the case. A

sketch contrasting scenarios in which a uid is compressed in which the system approach

would be used against those where the control volume approach would be used is shown in

Fig. 2.2. In summary,

system xed mass, closed, and

control volume potentially variable mass, open.

2.2 Macroscopic versus microscopic

In principle, we could solve for the forces acting on every molecule and use Newtons laws

to determine the behavior of systems. This is dicult for even modestly sized systems.

If we had a volume of 1 m

3

of gas at atmospheric pressure and temperature, we would

nd that it was composed of 2.4 10

25

molecules.

We would need six equations of motion for each molecule, three for x, y, z, position,

and three for u, v, w velocity. This would require then a total of 1.4 10

26

dierential

equations to solve simultaneously.

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.2. MACROSCOPIC VERSUS MICROSCOPIC 31

piston-cylinder compressor

system approach

control volume approach

system

ow in ow out

control

volume

Figure 2.2: Comparison of system (xed mass) and control volume (xed volume) approaches

in thermodynamics for two common scenarios: piston-cylinder compression (left) and com-

pression in a ow device whose details are not shown (right).

Even with our largest computers, this is impossible today. Note most desktop com-

puters only can store roughly 10

9

bytes of data in Random Access Memory (RAM).

We can however model the average behavior of the molecules statistically.

We can also use simple empirical relations which can be formally proved to capture

the statistical nature of the ow. This will be our approach.

classical thermodynamics will treat macroscopic eects only and ignore individual

molecular eects. For example molecules bouncing o a wall exchange momentum

with the wall and induce pressure. We could use Newtonian mechanics for each par-

ticle collision to calculate the net force on the wall. Instead our approach amounts to

considering the average over space and time of the net eect of millions of collisions on

a wall.

We will in fact assume that matter can be modelled as a

Continuum: the limit in which discrete changes from molecule to molecule can be

ignored and distances and times over which we are concerned are much larger than

those of the molecular scale. This will enable the use of calculus in our continuum

thermodynamics.

The continuum theory can break down in important applications where the length and time

scales are of comparable magnitude to molecular time scales. Important applications where

the continuum assumption breaks down include

rareed gas dynamics of the outer atmosphere (relevant for low orbit space vehicles),

and

CC BY-NC-ND. 04 May 2012, J. M. Powers.

32 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

nano-scale heat transfer (relevant in cooling of computer chips).

To get some idea of the scales involved, we note that for air at atmospheric pressure and

temperature that the time and distance between molecular collisions provide the limits of

the continuum. Under these conditions, we nd for air

length > 0.1 m, and

time > 0.1 ns,

will be sucient to use the continuum assumption. For denser gases, these cuto scales are

smaller. For lighter gases, these cuto scales are larger. Details of collision theory can be

found in advanced texts such as that of Vincenti and Kruger.

1

They show for air that the

mean free path is well modeled by the following equation:

=

M

2Nd

2

. (2.1)

Here, M is the molecular mass, N is Avogadros number, and d is the molecular diameter.

Example 2.1

Find the variation of mean free path with density for air.

We turn to Vincenti and Kruger for numerical parameter values, which are seen to be M =

28.9 kg/kmole, N = 6.02252 10

23

molecule/mole, d = 3.7 10

10

m. Thus,

=

_

28.9

kg

kmole

_

_

1 kmole

1000 mole

_

2

_

6.02252 10

23 molecule

mole

_

(3.7 10

10

m)

2

, (2.2)

=

7.8895 10

8 kg

molecule m

2

. (2.3)

Note that the unit molecule is not really a dimension, but really is literally a unit, which may well

be thought of as dimensionless. Thus, we can safely say

=

7.8895 10

8 kg

m

2

. (2.4)

A plot of the variation of mean free path as a function of is given in Fig. 2.3. Vincenti and Kruger

go on to consider an atmosphere with density of = 1.288 kg/m

3

. For this density

=

7.8895 10

8 kg

m

2

1.288

kg

m

3

, (2.5)

= 6.125 10

8

m, (2.6)

= 6.125 10

2

m. (2.7)

1

W. G. Vincenti and C. H. Kruger, 1965, Introduction to Physical Gas Dynamics, John Wiley, New York,

pp. 12-26.

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.3. PROPERTIES AND STATE OF A SUBSTANCE 33

0.01 0.1 1 10

10

-7

10

-6

10

-5

10

-4

10

-8

0.001

(m)

(kg/m

3

)

atm

1.288 kg/m

3

atm

~ 6.125 x 10

-8

m

Figure 2.3: Mean free path length, , as a function of density, , for air.

Vincenti and Kruger also show the mean molecular speed under these conditions is roughly c = 500 m/s,

so the mean time between collisions, , is

c

=

6.125 10

8

m

500

m

s

= 1.225 10

10

s. (2.8)

2.3 Properties and state of a substance

We dene

Phase: a quantity of matter that is homogeneous throughout, and

Phase Boundaries: interfaces between dierent phases.

An example of a single phase is ice. Another single phase is liquid water. A glass of ice

water is a two-phase mixture with the phase boundaries at the edge of each ice cube.

We next dene (circularly)

State: condition described by observable macroscopic properties, and

Property: quantity which only depends on the state of the system and is independent

of the history of the system.

Examples of properties include temperature and pressure. Two states are equivalent if they

have the same properties. So if state 1 is dened by temperature T

1

and pressure P

1

, and

state 2 is dened is by temperature T

2

and P

2

, state 1 is equivalent to state 2 i (that is, if

and only if) T

1

= T

2

and P

1

= P

2

.

There are two important classes of properties we consider in thermodynamics:

CC BY-NC-ND. 04 May 2012, J. M. Powers.

34 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

Extensive Property: a property which depends on the mass (or the extent) of the

system, example extensive properties include mass, total volume, total energy, and

Intensive Property: a property which is independent of the mass of the system.

Example intensive properties include temperature and pressure.

In general, if you cut a system in half and re-measure its properties, intensive properties

remain unchanged, while extensive properties are cut in half. Properties are dened for

systems which are in

Equilibrium: state in which no spontaneous changes are observed with respect to

time.

We actually never totally achieve equilibrium, we only approximate it. It takes innite time

to achieve nal equilibrium. In this class we will mainly be concerned with two types of

equilibrium:

Mechanical equilibrium: characterized by equal pressure, and

Thermal equilibrium: characterized by equal temperature.

A third type of equilibrium is chemical equilibrium, which we will not consider here, and is

characterized by equal chemical potentials.

A dicult conceptual challenge of thermodynamics is to reckon with two systems initially

at their own equilibria, to bring them into contact so that they nd a new equilibria. How to

do this without consideration of time can be dicult. Another branch of thermodynamics,

which we will consider only briey in this course is

Non-equilibrium thermodynamics: branch of thermodynamics which considers

systems often far from equilibrium and the time-dynamics of their path to equilibrium.

We will go to great eort to construct a thermodynamics which is generally not burdened

with time. Occasionally we will bring time into our problems. Unfortunately, ignoring time

occasionally requires some mental contortions, as seen in the next section.

2.4 Processes and cycles

Often systems undergo a

Change of State: implies one or more properties of the system has changed.

How these properties would change outside of time is curiously outside the framework of

equilibrium thermodynamics! The best way to think of them is that the changes are slow

relative to the underlying molecular time scales. Fortunately, this will allow us to do a wide

variety of problems of engineering relevance.

We also dene a

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.5. FUNDAMENTAL VARIABLES AND UNITS 35

Process: a succession of changes of state.

We assume our processes are all suciently slow such that each stage of the process is near

equilibrium. Certain common processes are given special names, based on the Greek

,

o,

isos, meaning equal:

isothermal: constant temperature,

isobaric: constant pressure, and

isochoric: constant volume.

An important notion in thermodynamics is that of a

cycle: series of processes which returns to the original state.

The cycle is a thermodynamic round trip.

2.5 Fundamental variables and units

We will mainly use the Syst`eme International (SI) units in this course. Occasionally, we

will use the English Engineering system of units. As found in US National Institute of

Standards and Technology (NIST) documents, the important fundamental base SI units,

and corresponding English units are

mass:

kilogram (kg): a mass equal to the mass of the international prototype of the

kilogram (a platinum-iridium bar stored in Paris), roughly equal to the mass of

one liter of water at standard temperature and pressure, and

pound mass: (lbm),

length:

meter (m): the length of the path traveled by light in vacuum during a time

interval of 1/299792458 of a second, and

foot (ft),

time:

second: (s) the duration of 9192631770 periods of the radiation corresponding to

the transition between the two hyperne levels of the ground state of the cesium

133 atom, and

second: (s) English time units are identical to those of SI,

CC BY-NC-ND. 04 May 2012, J. M. Powers.

36 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

temperature: an equilibrium property which roughly measures how hot or cold an

object is. Note our senses are poor judges of temperature. Consider snow and air in

thermal equilibrium at 20

F. Usually, it is possible to keep your bare hands warm

for many hours at 20

F if you are otherwise dressed warmly. However, if you place

your bare hand in a snow bank you for a few minutes, you have a danger of frostbite.

Yet both are at the same temperature. Why the dierence in sense? Our bodies

actually have more sensitivity to heat uxes instead of temperature; heat leaves our

body more rapidly when in contact with high density objects like snow relative to that

of low density objects like air. More fundamental than common units such as

F are

so-called absolute temperature units:

Kelvin: (K) the fraction 1/273.16 of the thermodynamic temperature of the

triple point of water, and

Rankine: (

R).

2.6 Zeroth law of thermodynamics

In this class we are taking the axiomatic approach. Recall that an axiom cannot be proven.

It is a statement whose truth can be ascertained only by comparison with experiment.

The axiom can be disproved by a single negative experiment. The so-called zeroth law of

thermodynamics is the axiom which is probably most fundamental. It was formalized after

the so-called rst and second laws, and so it is called the zeroth law. Perhaps if a more

fundamental axiom were discovered, it would be called the 1

st

law of thermodynamics?

Zeroth law of thermodynamics: When two bodies have equality of temperature

with a third body, then they have equality of temperature.

The origins of the zeroth law are murky. Sommerfeld

2

attributes the notion to R. H. Fowler

in a 1931 review of a thermodynamics book. Fowler and Guggenheim explicitly introduce

the term zeroth law of thermodynamics later.

3

The equivalent statement in mathematical logic is that if x = y and x = z, then y = z.

Denition of the zeroth law enables the use of a thermometer as a measurement device.

A scale however needs to be dened. The old metric temperature scale, Celsius (

C), was

dened so that

0

C is the freezing point of water, and

100

C is the boiling point of water.

2

A. Sommerfeld, 1956, Thermodynamics and Statistical Mechanics, Lectures on Theoretical Physics,

Vol. V, Academic Press, New York, p. 1.

3

R. Fowler and E. A. Guggenheim, 1939, Statistical Thermodynamics: A Version of Statistical Mechanics

for Students of Physics and Chemistry, Cambridge University Press, Cambridge, p. 56.

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.7. SECONDARY VARIABLES AND UNITS 37

These quantities varied with pressure however, so that dierent values would be obtained

on top of a mountain versus down in the valley, and so this is not a good standard. The

modern Celsius scale is dened to be nearly the same, but has

0.01

C as the so-called triple point of water, and

273.15

C as absolute zero in K.

The triple point of water is dened at the state where three phase of water (solid, liquid, and

gas) are observed to co-exist. The transformation between the absolute Kelvin scale and the

Celsius scale is given by

K =

C + 273.15. (2.9)

The English equivalents are degrees Fahrenheit (

Rankine (

T(

R) = 1.8T(K), T(

F) = 1.8T(

C) + 32, T(

F) = T(

R) 459.67. (2.10)

2.7 Secondary variables and units

Many units can be derived from the base units. Some important units for thermodynamics

include

Force: This unit is dened from Newtons second law, F = m d

2

x/dt

2

.

Newton: (N), 1 N = 1

kg m

s

2

, and

pound force: (lbf).

Force is straightforward in SI units. It is more confusing in English units, where the

so-called gravitational constant g

c

is often introduced. In SI units, g

c

= 1. However in

English units, the law for force is better stated as

F =

1

g

c

m

d

2

x

dt

2

. (2.11)

Now, 1 lbf is induced by a mass of 1 lbm in places where local gravitational acceleration

is g = 32.1740 ft/s

2

. So if we have a simple statics problem where the acceleration

d

2

x/dt

2

= g, we then get

F =

1

g

c

mg. (2.12)

If we are at a location where g = 32.1740 ft/s

2

, we must have

1 lbf =

(1 lbm)

_

32.1740

ft

s

2

_

g

c

. (2.13)

CC BY-NC-ND. 04 May 2012, J. M. Powers.

38 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

Thus,

g

c

= 32.1740

lbm ft

lbf s

2

. (2.14)

Example 2.2

If the local gravitational acceleration is 32.0 ft/s

2

, what is the weight W of an object with mass

of m = 1000 lbm.

W = F =

1

g

c

mg =

1

32.1740

lbm ft

lbf s

2

(1000 lbm)

_

32.0

ft

s

2

_

= 994.59 lbf. (2.15)

Energy: roughly speaking, the ability to do work, found from the product of force

and distance.

Joule: (J), 1 J = 1 (N m), and

foot-pound force: (ft lbf).

Specific Volume: the volume per unit mass, known as v = V/m.

_

m

3

kg

_

, and

_

ft

3

lbm

_

.

Density: the mass per unit volume, the inverse of specic volume = m/V .

_

kg

m

3

_

, and

_

lbm

ft

3

_

.

Note also that

v =

1

, =

1

v

. (2.16)

Pressure: the lim

A0

F/A where A is the cross-sectional area and F is the force

acting on that area. In thermodynamics, we are almost always concerned with the

absolute pressure as opposed to the gauge pressure. Most common pressure gauges do

not measure the absolute pressure; instead they measure the dierence between the

absolute pressure and the atmospheric pressure. The two are related via the formula

P

gauge

= P

absolute

P

atm

. (2.17)

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.7. SECONDARY VARIABLES AND UNITS 39

We nearly always interpret P as an absolute pressure, so we could also say

P

gauge

= P P

atm

. (2.18)

Pascal: (Pa), 1 Pa = 1 N/m

2

; note other common units are 1 bar = 10

5

Pa,

1 atm = 1.01325 10

5

Pa = 101.325 kPa = 0.101325 MPa, and

(psia): 1 psia = 1 lbf/in

2

. 1 atm = 14.696 psia. The a denotes the absolute

pressure as opposed to the gauge pressure. The units psig refer to a gauge

pressure.

The SI unit is named after Blaise Pascal, see Fig. 2.4, the French polymath who

Figure 2.4: Blaise Pascal (1623-1662), French scientist and philoso-

pher who considered manometry, among other diverse topics; image from

http://www-history.mcs.st-and.ac.uk/history/Biographies/Pascal.html.

conducted early scientic experiments with manometers, a common measuring device

for pressure, see Fig. 2.5. There are a variety of styles of manometers. Here, a pipe

containing uid at pressure P and density has a small tube with cross sectional area

A connecting it to the outside atmosphere at a dierent pressure P

atm

. The length H is

easily measured. The gravitational acceleration is g and is in the negative y direction.

Because P > P

atm

, the manometer uid is pushed up. However, it nds a mechanical

equilibrium where the weight of the manometer uid balances the net force induced

by the pressure dierential.

The gure includes a cutaway with a free body diagram. The interior uid exerts a

positive force of PA on the manometer uid in the cutaway. The atmosphere exerts

another force of P

atm

A in the negative direction. The third force is the weight of the

uid: mg. Thus, Newtons second law tells us

m

d

2

y

dt

2

..

=0

= PAP

atm

A mg. (2.19)

CC BY-NC-ND. 04 May 2012, J. M. Powers.

40 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

P

atm

H

g

P A

P A

atm

Fluid at P,

A

mg = V g = A H g

y

Figure 2.5: Manometer sketch.

Now, we are concerned with cases which are static, in which case the acceleration

d

2

y/dt

2

= 0. Thus, we require a force balance, i.e. mechanical equilibrium, which is

achieved when

0 = PAP

atm

A mg, (2.20)

PA = P

atm

A + mg. (2.21)

Now, mg = V g, where V is the volume of the uid in the cutaway. Obviously from

the geometry, we have V = AH, so mg = AHg. Thus,

PA = P

atm

A + AHg, (2.22)

P = P

atm

+ gH. (2.23)

Or

P = P P

atm

= P

gauge

= gH. (2.24)

Example 2.3

A manometer gives a reading of H = 2 ft in a region where local g = 32.2 ft/s

2

. The working

uid has specic volume v = 0.0164 ft

3

/lbm. The atmospheric pressure is P

atm

= 14.42 lbf/in

2

=

14.42 psia. Find the uid pressure.

We know that in the SI system.

P = P

atm

+ gH. (2.25)

In terms of specic volume, recalling that = 1/v, we have

P = P

atm

+

gH

v

. (2.26)

CC BY-NC-ND. 04 May 2012, J. M. Powers.

2.7. SECONDARY VARIABLES AND UNITS 41

The challenge here is really the English units. A fair way to approach English units is to replace g by

g/g

c

in every formula. Thus, in English units, we have

P = P

atm

+

1

v

g

g

c

H. (2.27)

So our uid pressure is

P = 14.42

lbf

in

2

+

1

0.0164

ft

3

lbm

_

32.2

ft

s

2

32.1740

lbm ft

lbf s

2

_

(2 ft)

_

1 ft

12 in

_

2

= 15.27

lbf

in

2

= 15.27 psia. (2.28)

CC BY-NC-ND. 04 May 2012, J. M. Powers.

42 CHAPTER 2. SOME CONCEPTS AND DEFINITIONS

CC BY-NC-ND. 04 May 2012, J. M. Powers.

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