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(Vˆ),
specific internal energy (Û), refractive index (R), and
other variables (Ĥ, Ĝ, Ŝ, Â) 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 ,Vˆ ); U = U (T ,Vˆ )
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 A’s = Gas B’s + 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 + ρghi
RTi = Pi (V)
Pi
R = constant per mole
V i = # of runs

Ti

ρ: 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

1907 steam engines in a steamship

1827 wooden paddle-wheel boat using steam Engines 15% efficiency

2002 a steam paddle boat

sailed in Rhine river, GE
1910 later steam turbine with 30% efficiency 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.

Don’t worry, it won’tL´eonard

Sadi Nicolas start to get complicated or
Carnot
scientific now!
(1796-1832)
We’ll 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 (π)
(5) Others, such as density, refractive index, Ĥ, Ĝ, Ŝ, Â, etcetera
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 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.
ΔS total = ΔS system + ΔS surr > 0 for irrevesible process (or isolated cyclic)
ΔS rev
total
= 0 for reversible process (or isolated cyclic)

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 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 Max Karl Ernst Ludwig

Kelvin) (1824-1907) Planck (1858-1947)
Lack of an condenser here !
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 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 21
1822-1888
 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
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 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, ΔS: ΔS = dQT
r

Claisius proved the following from Carnot's cycle:

dQ
∫ T ≤ 0 in an arbitrary cycle
Irreversible and isolated process:
ΔS ≥ 0 S is a state function

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 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”

Highly ordered Disordered

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(Low entropy)
 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 Entropy = S = k (log Ω); k: Boltzman ' s constant
i+1
. Ω : probability distribution of one state or multisicity
i
ni !
. Ω=
i-1 n1 !..........nn !
n1...ni ...nn : molecules in each Q.M . state (i )
N = n1 + …+ nn : total molecules in the system ( crystal )
lowest
Q.M. state (i)

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 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?

Number (#) Total # of Probability of the specific

Case of states states state to be happened
(ω) (Ω) (Ω−1)
-1
Tossing 10 coins 2 210 10
(2 )
-1
Tossing 10 dices 6 610 (610)

24 24 -1
Moving 1-mole molecules in box 10 1010 (1010 )

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

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

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 (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

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

⎛ x1 ⎞
⎜ ⎟
U = f (T , P, x ) ⎜ 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 .

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 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)

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 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 )

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 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), ΩN
(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).
z Ω1
P1
1 ⎛ r1 ⎞ ⎛ Ω1 ⎞ ⎛ P1 ⎞
Ω2
r1 ⎜ 2⎟ ⎜ 2⎟ ⎜ 2⎟
r Ω P
2 r =⎜ ⎟ Ω =⎜ ⎟ P =⎜ ⎟
N N N

r2 P2 ⎜M⎟ ⎜ M ⎟ ⎜ M ⎟
y ⎜ n⎟ ⎜ n⎟ ⎜ n⎟
⎝r ⎠ ⎝Ω ⎠ ⎝P ⎠

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 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.

z All pressures and temperatures are constant in all

places for both states (SS and ES).

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 Review-15
Comments on Development of Thermodynamics
A: Formal definitions and thermodynamics property relationships such as Legendre’s
transformation; Chain rules; Triple product rule; Euler theroem; Maxwell equations;
Conservations of mass; Energy Classical Thermodynamics
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. It’s very accurate
Theorems Molecular Thermodynamics
and soundThermodynamics
B fundamentals but application is rare. (Prausnitz textbook) C

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
coefficient liquid models.Application
(Sandler to practical7,8,9,10,11,12)
Chapters industrial problems D

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.
supplements, pharmaceutics, numerical solutions with databank
(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)

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 Review-16
Time-Table and Milestones of Thermo-dynamics
• 1660 Boyle PV=constant at constant T
• 1687 Newton principle of work
• 1714 Fahrenheit Fahrenheit temperature scale
• 1742 Celsius Celsius temperature scale
• 1768 Watt steam engine
• 1787 Charles P ∝ T at constant V
• 1798 Thompson conversion of work to heat
• 1802 Gay-Lussac V ∝ T at constant P
• 1803 Henry Henry’s law
• 1805 Dalton total pressure = sum of partial pressures
• 1811 Avogadro Avogadro’s number
• 1824 Carnot thermal efficiency of heat engines, 1st law
• 1834 Clapeyron dP/dT of two phase transition equilibrium
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• 1842 Joule Joule’s mechanical equivalent of heat, 1st law
• 1848 Kelvin thermodynamic temperature scale
• 1854 Joule, Thomson Joule-Thomson coefficient
• 1865 Clausius defined entropy, 2nd law
• 1873 van der Waals equation of state and corresponding states
• 1875 Gibbs thermodynamic fundamental relations, μ
• 1881 Ponyting Poynting equation
• 1900 Onnes virial equation
• 1901 Lewis defined fugacity
• 1906 Nerst 3rd law of thermodynamics
• 1906 van Laar van Laar equation
• 1907 Lewis defined activity
• 1924 Lennard Jones Lennard-Jones potential energy and forces

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• 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
• Any New Recently ???
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particles have wave-like properties
wave equation
defined regular solution
steam tables
Wohl’s 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
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 Review-17

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