Thermodynamics

01 Introduction

Prof. Dr.-Ing. Manfred J. Hampe

Technische Universität Darmstadt
Thermal Process Engineering
hampe@tu-darmstadt.de

WS 2016/17

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 1/31 – 1 / 18

 1.1 Thermodynamics

➠ What does thermodynamics mean?

➟ Thermodynamics comes from
the Greek language:
➢ θ"ρµη = therme = heat
➢ δ&ναµις = dynamis = force
➟ Thermodynamics is the science
behind the steam engine, the
device that caused the first in-
dustrial revolution.

Source: [1]

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 2/31

 1.1 Thermodynamics

➠ What does thermodynamics mean?

➟ Thermodynamics comes from
the Greek language:
➢ θ"ρµη = therme = heat
➢ δ&ναµις = dynamis = force
➟ Thermodynamics is the science
behind the steam engine, the
device that caused the first in-
dustrial revolution.
➟ Thermodynamics deals with the
question how to turn heat into
work.
Source: [1]

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 3/31

 1.1 Thermodynamics

➠ What does thermodynamics mean?

➟ Thermodynamics comes from
the Greek language:
➢ θ"ρµη = therme = heat
➢ δ&ναµις = dynamis = force
➟ Thermodynamics is the science
behind the steam engine, the
device that caused the first in-
dustrial revolution. Source: [2]

➟ Thermodynamics deals with the

question how to turn heat into
work.
➟ Modern engines rely heavily on
thermodynamics: E. g. the Trent
1000
Source: [3]

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 4/31

 1.1 Thermodynamics

Source: [4]

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 5/31

 1.1 Thermodynamics

Thermodynamics is based on two laws and two theorems:

➠ The first law of thermodynamics (deals with energy)

➠ The second law of thermodynamics (deals with entropy)
➠ Nernst’s heat theorem
➠ Nernst’s theorem of the unattainablity of absolute zero

Fundamental to these While other disciplines have no idea

disciplines: what’s going on.

➠ Biology C. P. Snow: The two cultures [5]

➠ Chemistry
➠ Physics
➠ Geology
➠ Materials science
➠ Engineering
Source: [6]

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 6/31

 1.2 Preliminary concepts

From Lewis and Randall, Thermodynamics [7]:

➠ The fascination of a growing science lies in the work of the pioneers at the
very borderland to the unknown, but to reach this frontier one must pass
over well-travelled roads; of these one of the safest and surest is

the broad highway of thermodynamics.

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 7/31

 1.2 Preliminary concepts

From Lewis and Randall, Thermodynamics [7]:

➠ The fascination of a growing science lies in the work of the pioneers at the
very borderland to the unknown, but to reach this frontier one must pass
over well-travelled roads; of these one of the safest and surest is

the broad highway of thermodynamics.

➠ Science has its cathedrals, built by the efforts of a few architects and of
many workers. In these loftier monuments of scientific thought a tradition
has arisen whereby the friendly usages of colloquial speech give way to a
certain severity and formality. While this may sometimes promote

precise thinking,
it more often results in

the intimidation of the neophyte.

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 8/31

 1.2. Preliminary concepts
Thermodynamic systems

Universe

System

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 9/31

 1.2. Preliminary concepts
Thermodynamic systems

The system

➠ has a boundary
➠ has a control volume
➠ has a control surface

Isolated system Closed system Open system

➠ no mass trans- ➠ no mass trans- ➠ mass trans-

fer across the fer across the fer across the
boundary boundary boundary
➠ no heat trans- ➠ heat transfer ➠ heat transfer
fer across the across the across the
boundary boundary boundary

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 10/31

 1.2. Preliminary concepts
Thermodynamic systems
Piston-cylinder assembly:

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 11/31

 1.2. Preliminary concepts
Thermodynamic systems
Open System:

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 12/31

 1.2. Preliminary concepts
Thermodynamic properties

Properties Piston-cylinder assembly

(a ) Temperature T1
(b ) Pressure P1
(c ) Volume V1
(d ) Amount of substance n1
(e ) Molar volume v1

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 13/31

 1.2. Preliminary concepts
Thermodynamic properties

Properties Piston-cylinder assembly

(a ) Temperature T1
(b ) Pressure P1
(c ) Volume V1
(d ) Amount of substance n1
(e ) Molar volume v1

Intensive properties

➠ Are homogeneous functions of zeroth degree

λ0 · f = f (λx 1 , λx 2 , . . .)

➠ Do not depend on the size of the system

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 14/31

 1.2. Preliminary concepts
Thermodynamic properties

Properties Piston-cylinder assembly

(a ) Temperature T1
(b ) Pressure P1
(c ) Volume V1
(d ) Amount of substance n1
(e ) Molar volume v1

Extensive properties

➠ Are homogeneous functions of first degree

λ1 · g = g(λx 1 , λx 2 , . . .)

➠ Do depend on the size of the system

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 15/31

 1.2. Preliminary concepts
Processes

Adiabatic Isothermal Isobaric Isochoric

δι+ = through /σος = same /σος = same /σος = same
βα-νω = to walk θ"ρµη = heat βαρ&ς = heavy χορ-ον = space
privative a ! negation
The temperature The pressure The volume
No heat trans- of the system re- of the system of the system
fer across the mains constant remains constant remains constant
system boundary

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 16/31

 1.2. Preliminary concepts
Hypothetical paths

State functions
➠ State functions only depend on the state of the system
➠ State functions are independent of the path from state 1 to state 2
➠ Typical state functions are
➟ Volume
➟ Energy
➟ Pressure
➟ Temperature

Path functions
➠ Path functions depend on the path from state 1 to state 2
➠ Typycal path functions are
➟ Work
➟ Heat flux

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 17/31

 1.2. Preliminary concepts
Phases of matter
Phases have

➠ The same temperature at every position within a phase

➠ The same pressure at every position within a phase
➠ The same composition at every position within a phase
➠ The same density at every position within a phase
➠ A phase boundary

Solid Liquid Gas

➠ Either crystalline or
amorphous
➠ Fixed shape
➠ Atoms are at fixed
positions and vibrate
about the positions
➠ Several solid phases
can coexist in a system
➠ Fixed Volume
➠ No shape
➠ Molecules are not at
fixed positions and
move freely with short
free pathways
➠ Several liquid phases
can coexist in a system
➠ Occupy all the volume
of the system minus
the volumes of liquid
and solid phases
➠ No shape
➠ Molecules move free-
ly with long free pa-
thways
➠ There is only one gas
phase in a system

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 18/31

 1.2. Preliminary concepts
Length scales

Thermodynamics

➠ Is a macroscopic theory
➠ Does not know anything about molecules or atoms
➠ Deals with systems of „sufficient“ size

On the molecular scale

➠ Molecules and atoms do exist
➠ Explanations of macroscopic behavior can be given

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 19/31

 1.2. Preliminary concepts
Dimensions and units
Dimensions

Physical properties have dimensions

➠ The dimension of the volume V is length 3
➠ The dimension of the temperature T is temperature
➠ The dimension of the pressure P is timemass
·length
➠ The dimension of amount of substance n is amount of substance
➠ The dimension of the molar volume v is amountlength
of substance
3

Consistent units have to be used Units

The Système International (SI) uses The SI measures the

➠ Meter for length ➠ Volume in m3
➠ Kilogram for mass ➠ Temperature in K
➠ Second for time ➠ Pressure in kg/(s2 m)
➠ Mole for amount of substance ➠ Amount of substance in mole
➠ Kelvin for temperature ➠ Molar volume in m3 /mol

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 20/31

 1.3. Measured thermodynamic properties: Mass

➠ The SI-unit of mass is the kilogram, kg.

➠ In the US, mass is given in pound-weight, lbw .
Beware:
➠ In the US, force is given in pound-force, lbf
➠ If pound-weight and pound-force are used in the same equation, the
dimensional conversion factor of gravity,

lbw ft
g c = 32.174
lbf s2

is needed

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 21/31

 1.3. Measured thermodynamic properties: Volume

The extensive property volume The intensive properties molar

volume and specific volume
is measured in
➠ Cubic meter, m 3 are measured in m3 /mol and m3 /kg
➠ Liter, L = dm3 ➠ If the phase is homogeneous:
➠ Milliliter, mL
➠ Nanoliter, nL V 1 V 1
v= = ; v̂ = =
➠ Picoliter, pL n c m ρ

with c = concentration
and ρ = density
➠ if the phase is inhomogeneous,
the molar and specific volumes
are defined as field variables:
V V
v = lim ; v̂ = lim
V →0 n V →0 m

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 22/31

 1.3. Measured Thermodynamic Properties: Temperature

➠ The skin has sensors for hotness or coldness: We can estimate temperatures
➠ We see hotness when looking at red glowing or white glowing steel
➠ We measure temperature with a thermometer
➠ There are several temperature scales: Kelvin, and Celsius

T [◦C] = T [K] − 273.15 K

➠ Fahrenheit in the US
9
T [◦ F] = T [◦C] · + 32
5

➠ If TA > TB and TB > TC then TA > TC

➠ In thermal equilibrium: TA = TB = TC

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 23/31

 1.3. Measured Thermodynamic Properties: Temperature

1 3
T ∝ mv⃗2 = ekin ; ekin = kT
2 2
Boltzmann constant k = 1.38 × 10−23 J/K/molecule

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 24/31

 1.3. Measured thermodynamic properties: Pressure

Molecular picture of pressure Molecules hitting the piston

change in momentum
= mvz − (−mvz )
molecule that hits the piston
= 2mvz

N "
1 ! d(mvz )
#
P=
A i=1 dt
Units of pressure:
kg N J
1 Pa = 1 2
=1 2
=1
ms m m3

1 bar = 105 Pa

Obsolete:

1 atm = 760 mmHg = 1.013 25 bar

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 25/31

 1.3. Measured thermodynamic properties: The ideal gas

The law of ideal gases

Equation of state for ideal gases:

RT nRT
p= =
v V

Some common values for the gas constant R:

8.314 J/(mol K)
0.083 14 L bar/(mol K)
0.082 06 L atm/(mol K)
1.987 cal/(mol K)

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 26/31

 1.3 Measured thermodynamic properties
Example 1.1: Determination of ideal gas law

Show that the ideal gas model can be derived from the molecular definition of pressure, Equation
(1.7). The molecular relationship between temperature and kinetic energy, Equation (1.5), is useful.

SOLUTION: The definition of pressure is given by Equation (1.7):

N "
1 ! d(mvz )
#
P=
A i=1 dt i

The rate of change in z momentum of any particular molecule can be separated into two parts, as
follows:
d(mvz ) change in momentum collisions
$ % $ %
= =
dt collision of molecule with piston time

The first term on the right-hand side of Equation (E1.1A) is given by Equation (1.6):

change in momentum
$ %
= mvz − (−mvz ) = 2mvz
collision of molecule with piston

The second term can be obtained if we realize a molecule must travel a length, l , to collide with the
piston. Hence the rate of collisions can be approximated by:

collisions Avz
$ %
vz
= =
time l V

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 27/31

 1.3 Measured thermodynamic properties
Example 1.1: Determination of ideal gas law

Substituting Equations (E1.1B) and (1.6) into Equation (E1.1A), and then using Equation (E1.1A) in
Equation (1.7) gives:
N " N /2 & 2 '
1 ! d(mvz ) 1 ! 2mvz )
#
P= =
A i=1 dt i A i=1 V i

where we have divided the total number of molecules in the system by 2 since the molecules heading
away from the piston with a velocity −vz will not hit it. Thus, we do not count them in the calculation
of the pressure. We can rewrite Equation (E1.1C) by using the average mean speed instead of summing
over all the individual velocities. The average mean speed is given by the following relation:
N /2
! N 2
(vz2 )i = v
i=1
2 z

Inserting this expression into Equation (E1.1C), we get:

mN 2
P= v
V z

Since the molecules are equally likely to move in any of three directions, we can replace the speed in
the z direction with the total speed v⃗, as follows:
1 2
vz2 = v⃗
3

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 28/31

 1.3 Measured thermodynamic properties
Example 1.1: Determination of ideal gas law

The factor of 3 arises since there are three possible directions of motion. Plugging in Equation (E1.1E)
into (E1.1D) gives:
( )
2N 1 2N
* +
molecular
P= mv⃗2 = e
3V 2 3V kin

where Equation (1.4) was used.

Finally substituting Equation (1.5) gives the law of ideal gases:

Law of ideal gases

N kT nRT
P= =
V V

where R = kNA and NA is Avogadro’s number.

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 29/31

 1.4 Equilibrium

Mechanical equilibrium Thermal equilibrium

Psys = Psurr Tsys = Tsurr

Phase equilibrium

T liquid = T gas
P liquid = P gas
escaping tendency of component i liquid = escaping tendency of component i gas
escaping tendency to be defined later

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 30/31

 References

The lecture follows Koretsky [8]. Further reading: Truesdell [9], Callen [10], Kondepudi and Prigogine [11]

[1] THURSTON, Robert H. , A schematic of Watt’s steam engine printed in a 1878 book. 1887. URL: https://upload.wikimedia.org/
wikipedia/commons/5/5c/Watt_steam_pumping_engine.JPG. History of the growth of the steam engine, D. Appleton & Co.
[2] KUNZLER, Joe A. , A Trent 100 in Lumix Dynamic Art HDR. 15. Juni 2012. URL: https://www.flickr.com/photos/avgeekjoe/
9048198726/ (besucht am 2016-02-13).
[3] CACTUSBILLAZ, , Rolls-Royce Trent 1000 N787RR. 14. Jan. 2014. URL: https://www.flickr.com/photos/avgeekjoe/9048198726/
(besucht am 2016-02-13).
[4] TODAY IN SCIENCE HISTORY, , Science owes more to the steam engine than the steam engine owes to science. Attributed to Lawrence
J. Henderson. 2016. URL: http://todayinsci.com/H/Henderson_Lawrence/HendersonLawrence-SteamQuote800px.htm (besucht am
2016-02-13).
[5] SNOW, C. P. , The two cultures. Cambridge University Press, 1959. ISBN: 0521457300.
[6] SCIENTIFIC AMERICAN, , Hrsg. Titlepage: CP Snow sitting on a bridge between Sciences and Humanities (Sep. 2009).
[7] LEWIS, G.N. , M. RANDALL, Thermodynamics. Hrsg. von K. S. PITZER und L. BREWER. 2. Aufl. McGraw Hill, 1961.
[8] KORETSKY, Milo D. , Engineering and chemical thermodynamics. 2. Aufl. Wiley, 2012. ISBN: 9780470259610.
[9] TRUESDELL, C. A. , The tragicomical history of thermodynamics 1822-1854. Hrsg. von M. J. KLEIN. Hrsg. von G. J. TOOMER. Studies in
the history of mathematics and physical sciences 4. New York: Springer, 1980. ISBN: 0387904034.
[10] CALLEN, H. B. , Thermodynamics and an Introduction to Thermostatistics. 2. Aufl. New York: John Wiley & Sons, Inc., 1986. ISBN:
8126508124.
[11] KONDEPUDI, Dilip , Ilya PRIGOGINE, Modern thermodynamics. Chichester: Wiley, 1998. ISBN: 0471973947.

– ©Prof. Hampe 2016 THE – 01 Introduction – 2016-09-05 01:06– 31/31