Chapter 1

Introduction to Thermodynamics

Chemical, Biochemical, and

Engineering Thermodynamics
4th Edition
Stanley I. Sandler, Univ. of Delaware
ISBN: 0-471-66174-0

Copyright 2007 by John Wiley & Sons, Inc. All rights reserved.

State Variables
By definition, state variable refers to intensive
variables of an equilibrium system, such as:
temperature (T), pressure (P), specific volume(V),
specific internal energy (), refractive index (R), and
other variables (, , , ) introduced in the systems
(heat engines, distillations, reactions, etcetera).
Clearly, state variable depends only on equilibrium
state of the system, not on the path by which the
equilibrium state was reached.

P = P(T ,V ); U = U (T ,V )
A pure fluid with single phase at equilibrium state (e.g.
steam sealed in a stainless steel cylinder) indicates that
if this fluid having specified T and V, it always have a
certain pressure P. What is P? We must either
determine P by experiment or know relationship
between T, V, and P. Scientific or engineering interest
is to make a lot measurements of P, V, and T to
develop a mathematical volumetric equation of state.
Similarly, measurements of U, V, and T are made to
develop a thermal equation of state.

Stable and Unstable Processes

f1_3_1

Blocks in states (a) and (b) are stable to mechanical disturbances. The
delicately balanced block in state (c) is not.

Two observations for characteristics of natural processes:

(I) System free from forced flows will evolve to an equilibrium state.
(II) Once in equilibrium, system will never spontaneously evolve to a
non-equilibrium state unless a perturbation input.

Pressures in Mechanics and Thermodynamics

Frictionless piston
Pressure of Gas A equals to that of Gas B in the system

Gas As = Gas Bs + force of gravity on the piston divided by its surface area
f1_4_1

Dead Weight Pressure Tester

Ps

f1_4_2

Total pressure in textbook refers to absolute pressure. Note that

gauge pressures may be negative (in partially or completely
evacuated systems), zero, or positive. So that a gauge calibrated in
France may be error for pressure measurements in Taiwan.
Total pressure P = gauge pressure Ps + atmospheric pressure Pa

Constant-volume Ideal Gas Thermometer

1 bar
Pi = 1 bar + ghi
RTi = Pi (V)

Pi

R = constant per mole

i = # of runs

Ti
: density of Mercury
g: gravity
f1_4_3

Temperatures Indicated by Different Fluids

pg_24

t1_2_1

t1_2_2

t1_2_3

t1_2_4

t1_4_1

Water prepared at temperature T1 in an insulated container. By several experiments,

energies were spent in producing a final equilibrium temperature T2. It resembles
experimental steam engine boat observation of James Prescott Joule between 1837 and 1847

What is steam engine boat?

t1_5_1

Ships Driven By Engines

2010 showboat Branson in Table
Rock Lake, Branson, Missouri

1827 wooden paddle-wheel boat using steam Engines

1910 later steam turbine with 30% efficiency

1907 steam engines in a steamship

15% efficiency

2002 a steam paddle boat

sailed in Rhine river, GE
1912 later diesel engine 45% efficiency

Viewing the past to be able to see the future

e.g. The Propulsion of Sea-ships (Past, Present, Future)
Roman warship with sail and oars ~200 B.C.

Diesel engine powers electric generator that

drive a motor to move a propeller~2008

Hydrogen propulsion using a motor powered by

hydrogen cell for submarines shown as left ~2020?

A Milestone of Thermo-Dynamics
Even 50 years before the invention of the Otto motor,
in 1824 the Frenchman, Carnot (the 1st law inventor),
described a thermo-dynamic cyclic heat engine with
theoretically the highest possible efficiency.
Carnot Statement:
All irreversible heat engines between two heat reservoirs are less
efficient than a Carnot Engine operating between the same reservoirs.
All reversible heat engines between two heat reservoirs are equally
efficient with a Carnot engine operating between the same reservoirs.

Dont worry,
it wontLeonard
start to get
complicated or
Sadi Nicolas
Carnot
scientific now!
(1796-1832)
Well remain on Thermo-dynamics for beginners

Review-1
1.1 The Central Problems of Thermodynamics
It is to resolve engineering EQUILIBRIUM problems including
calculations of energy and phase equilibrium.
1.2 Equilibrium Definition
(1) T is constant throughout the system- Thermal Equilibrium
(2) P is constant throughout the system-Mechanical Equilibrium
(3) x is constant throughout the system or parts of the system
(4) No gradients in macroscopic state variables
1.3 The State Variables of The System
Typical state variables:
(1) Temperature (T)
(2) Pressure (P)
(3) Composition (x)
(4) Phase of gas, liquid, solid ()
(5) Others, such as density, refractive index, , , , , etcetera
5/28/2012

CH3003

18

Review-2
1.4 Three Laws of Thermodynamics
1st law: Total energy of the system plus the surrounding is
conserved. Most text books use the following internal energy
change (dU) assuming surrounding stays the same. It is no
kinetic energy, no potential energy and no friction loss, which is
reliable for the reversible process only.
dU = dQ + dW
dU = TdS PdV

2nd law: All processes occur at such that total entropy

change of the system plus the surrounding is positive.
S total = S system + S surr > 0 for irrevesible process (or isolated cyclic)
total
S rev
= 0 for reversible process (or isolated cyclic)

5/28/2012

CH3003

19

Review-3
Second Law in Kelvin-Planck Form: statement
It is impossible to construct a heat engine that, operating in a cycle,
produces no other effect than the absorption of energy from a reservoir
and the performance of an equal amount of work.

It is explainable that any heat engine efficiency is less than that

of the Carnot heat engine (the highest).

William Thomson (Lord

Kelvin) (1824-1907)
5/28/2012

Max Karl Ernst Ludwig

Planck (1858-1947)
Lack of an condenser here !
CH3003

20

Review-4
Second Law in Clausius Form: statement
No process is possible whose sole result is the transfer of heat from a body of
lower temperature to a body of higher temperature

It is impossible to construct a cyclical machine whose sole

effect is to transfer energy continuously by heat from one object
to another object at a higher temperature without the input of
energy by work.
Energy does not transfer spontaneously by heat from a cold
object to a hot object.
It is explainable for a refrigerator required a work (compressor)
to transfer heat from cold to hot reservoirs.
5/28/2012

Rudolf Clausius
CH3003
1822-1888

21

Review-5
Entropy Inventor (Clausius)
Entropy, S, is a state variable related to the second law
of thermodynamics
The importance of entropy grew with the development
of statistical mechanics (or statistical thermodynamics)
A main result is isolated systems tend toward disorder
and entropy is a natural measure of this disorder.

His conclusion:
The entropy of the universe tends to a maximum
5/28/2012

CH3003

22

Review-6
Entropy and Heat
Original formulation of entropy dealt with transfer
of energy by heat in a cyclic process.
Let dQr be the amount of energy transferred by
heat when a system follows a reversible path. The
change in entropy, S: S = dQT
r

Claisius proved the following from Carnot's cycle:

dQ
T 0 in an arbitrary cycle
Irreversible and isolated process:
S 0
S is a state function
5/28/2012

CH3003

23

Review-7
Another version of 2nd law: statement
The entropy of the universe increases in all natural processes
An equivalent statement of 2nd law is in any cyclic process
of an isolated system, the entropy will either increase or
remain the same with time.
Thus entropy gives information about the evolution of an
isolated system with time, it is said to give us the direction
of Time Arrow.
The amount of disorder of an isolated system increases with
time. It is impossible to go from a disordered system to an
ordered system without external interference.
Time Arrow
5/28/2012

Highly ordered
(Low entropy)

CH3003

Disordered
(High entropy)

24

Review-8
3rd law: Entropy of a perfect crystal is zero at a temperature of
zero degrees Kevin.
What is entropy ? It is not disorder and it is a measure of disorder.
On the Boltzmann theorem: If the substance is a perfect crystal at
T = 0 K, then all particles of the crystal is settled at the lowest
Quantum Mechanic state. This condition is the same for all particles.
i+2
i+1
.
i
.
i-1

Entropy = S = k (log );

k: Boltzman ' s constant

: probability distribution of one state or multisicity

=

ni !
n1 !..........nn !

n1...ni ...nn : molecules in each Q.M . state (i )

lowest

N = n1 + + nn : total molecules in the system ( crystal )

Q.M. state (i)

5/28/2012

CH3003

25

Review-9
On a statistical probability state:

Entropy is total # of states that to be possibly

happened in a system. What is the probability of an exception (state) happened in the system?
Case

Number (#)
of states

Total # of
states

210

()

Tossing 10 coins

()

Probability of the specific

state to be happened
(1)
-1
10
(2 )
-1

Tossing 10 dices

Moving 1-mole molecules in box

610

10

1010

24

(610)

24 -1

(1010 )

Q: A system contains N molecules and supposed # of states of one molecule is moving in

box, =10, what is entropy (S) of the system ?
N: Avogadro's number=6.23(10)23; Boltzmanns constant=1.381(10)-23
S = k (log ) = 1.381(10)-23 log(1010 ) = 1 ~ 10 J / K
24

5/28/2012

CH3003

26

(1) Entropy is measures of disorder and statistically always

increase.
(2) Entropy increases with the number of states.
(3) On the first law (energy conservation), Niagara falls
could flow upwards. But thanks for the entropy law
(arrow of time), it is impossible because of the lowest
probability.

Thermodynamic properties is AVERAGE BEHAVIOR of molecules

5/28/2012

CH3003

27

Review-10
1.5 Other Postulates for Thermodynamics
(a) Internal energy of the system can be in terms of x:

U = f (T , P, x )

x1

x2
x=
M

xn

(b) It is impossible to have an entropy meter, but you

could obtain S from CP and CV values, indirectly.
(c) It is impossible to have an internal energy meter as
well, but you could obtain U from CV .

5/28/2012

CH3003

28

Review-11
The Zero law of Thermodynamics
(d) It is not a mathematical function, but called Thermo Contacted Bodies
to measure coldness and hotness of two bodies, then determine whether
the systems are in thermal equilibrium or not.
(e) Thermodynamic properties have been used to measure temperature:
z Pressure of a gas at constant density (constant volume gas thermometry)
z Density (volume) of a liquid or solid (liquid in glass thermometer)
z Electrical resistivity (resistant thermometers, e.g. RTD thermometer)
z Electrical potential appearing across the junction of two dissimilar
metals (e.g. thermocouple)
z Vapor pressure of a pure liquid
z Intensity of thermal radiation (e.g. optical pyrometer)
z Vibration voltage of an electronic diode
z Magnetic change of the magnet
z Phase transition (e.g. liquid crystal thermometer)
5/28/2012

CH3003

29

Review-12
Both Q and W are time transit energies
(f) What is work? It is a line integral and path dependence.
state 2

Work = W = state 1 ( force) d (coordinate)

dW

path 1

dW

path 2

(g) What is heat? It is also path dependence.

state 2

Heat = Q = state 1 d (thermal energy )

5/28/2012

CH3003

30

Review-13
Macroscopic thermodynamics equilibrium state
(h) There is no variations in measured properties (T, P) with time and space.
z All macroscopic forces (e.g. thermal, mechanical, chemical, electrical,
interfacial, etc.) are in balance within the system.
z Coordinates of molecules, e.g. rN (position of N molecules), N
(orientation) and PN (momentum) are continuously changing but average
contributions do not. All these coordinates contribute to phase space.
z Average macroscopic properties (T, P, V, x) have no fluctuations for
systems (Number of molecules > 109 for gas, N > 103 for condensed).
1

z
P1

r1
r2

5/28/2012 x

2
2
P2

r1
2
r
N
r =
M
n
r

CH3003

1
2

N
=
M
n

P1
2
P
N
P =
M
n
P

31

Review-14
Equilibrium State (ES) and Steady State (SS)
Equilibrium State (ES) is useful for solving problems of
the fixed state and the steady systems.
z

Steady State (SS or called pseudo equilibrium state)

means that external force is still counted, in that case,
there may be a pressure (or temperature) difference
within the system. SS is a set including ES.

All pressures and temperatures are constant in all

places for both states (SS and ES).

5/28/2012

CH3003

32

Review-15
Comments on Development of Thermodynamics
A: Formal definitions and thermodynamics property relationships such as Legendres
transformation; Chain rules; Triple product rule; Euler theroem; Maxwell equations;
Classical
Thermodynamics
Conservations of mass; Energy
and Entropy
balances; Heat engines; Gibbs-Duhem and Gibbs(or Thermo-Physics)
A entropy calculations (Sandler
Helmholtz equations; Equlibrium rules including energy and
Chapters 2,3,4,5,6)
B: Using intermolecular
Statistical forces relationship to explain what is Thermodynamics. Its very accurate
Molecular Thermodynamics
Theorems
and soundThermodynamics
fundamentals but application
is rare. (Prausnitz
textbook)
C
B
C: Corresponding state theory, van der Waal, Redlich-Kwong and Peng-Robinson fugacity
coefficient equations of state; van-Larr, Margules, Wilson, NRTL, UniQuac, Unifac activity
practical7,8,9,10,11,12)
industrial problems
D
coefficient liquid models.Application
(Sandler to
Chapters
D: Assumming systems approximation to equilibrium or steady state, such as Chemical Vapor
Deposition or Plasma Deposition for TFT-LCD thin films; Biotechnology processing for health
UsingNeutraceutics.
numerical solutions
with databank
supplements, pharmaceutics,
(Sandler
Chapters 13,14,15)
E
E: Tools such as ASPEN Plus (i.e. Hysys) or ChemCad or SimSci (PRO-II) or PE2000; Databanks
such as DIPPR or ASOG. (Junior courses)
5/28/2012

CH3003

33

Review-16
Time-Table and Milestones of Thermo-dynamics

1660 Boyle
1687 Newton
1714 Fahrenheit
1742 Celsius
1768 Watt
1787 Charles
1798 Thompson
1802 Gay-Lussac
1803 Henry
1805 Dalton
1811 Avogadro
1824 Carnot
1834 Clapeyron

5/28/2012

PV=constant at constant T
principle of work
Fahrenheit temperature scale
Celsius temperature scale
steam engine
P T at constant V
conversion of work to heat
V T at constant P
Henrys law
total pressure = sum of partial pressures
Avogadros number
thermal efficiency of heat engines, 1st law
dP/dT of two phase transition equilibrium
CH3003

34

1842 Joule
1848 Kelvin
1854 Joule, Thomson
1865 Clausius
1873 van der Waals
1875 Gibbs
1881 Ponyting
1900 Onnes
1901 Lewis
1906 Nerst
1906 van Laar
1907 Lewis
1924 Lennard Jones

5/28/2012

Joules mechanical equivalent of heat, 1st law

thermodynamic temperature scale
Joule-Thomson coefficient
defined entropy, 2nd law
equation of state and corresponding states
thermodynamic fundamental relations,
Poynting equation
virial equation
defined fugacity
3rd law of thermodynamics
van Laar equation
defined activity
Lennard-Jones potential energy and forces

CH3003

35

1924 de Broglie
1926 Schrodinger
1929 Hildebrand
1936 Keenan and Keye
1946 Wohl
1949 Redlich-Kwong
1955 Pitzer
1958 Reid and Prausnitz
1964 Wilson
1968 Renon & Prausnitz
1969 Carnahan & Starling
1975 Lee & Kesler
1976 Peng-Robinson

particles have wave-like properties

wave equation
defined regular solution
steam tables
Wohls expansion of excess Gibbs energy
R-K equation of state
acentric factor
The properties of gases and liquids
Local composition model
Non-Random Two-Liquid theory
Hard-sphere equation of state
Generalized equation of state
P-R equation of state

Any New Recently ???

5/28/2012

CH3003

36

Review-17

5/28/2012

CH3003

37