화학적에너지 수송
Lecture Note 02-2:
Thermodynamics/ Heat/Work and Energy
화학적 에너지 수송을 이해하는데 필요한 학문
■ 화학공학의 기본적 지식
■ 열역학
■ 반응공학
수강생들의 다양한 Background 를 고려한 강의 진행 예정
열역학을 배우는 데 어려운 점
■ 열역학은 지금까지 알아온 사실 , 즉 “경험”을 추상적인 기호로
나타낸 학문이다 .
■ 따라서 , 어떤 개념을 이해하려고 할 때 정확히 정의되지 않고 , 일종의
Hypothesis 가 포함되는 경우가 많다 .
■ 따라서 , 이미 정리된 개념을 이해하는 것이 아니라 우리의 경험을
어떻게 수식으로 전개하였는가를 이해하는 것이 중요하다 .
Quote about the law of thermodynamics…
만일 당신이 알기 원한다면 , 모든 자연현상을 지배하는 단 하나의 사실이 있다는 것을 알 수 있다 .
이 법칙은 우리가 아는 한 예외가 전혀 없다 .
이 법칙은 에너지 보존법칙이라고 불린다 .
이 법칙은 에너지라고 일컫는 어떤 양이 존재함을 이야기하고 있는데 , 형태가 여러 가지로 변하더라도 전체 양이 변하지
않는다 .
이 법칙은 수학적으로 표현되는 가장 추상적인 개념이다 .
이 법칙은 어떤 일이 일어나더라도 변하지 않는 수학적인 양이 존재함을 의미한다 . 이 법칙은 어떤 메커니즘이나 기반이
든든한 이론을 의미하지 않는다 .
이 법칙은 자연이 어떤 속임수를 부리는지 몰라도 모든 일이 끝나고 나서 우리가 숫자를 계산하고 나면 그 값이 같다는
이상한 사실을 말한다 .
無에서 有를 창조할 수 없다 !
Robert Feynman
1965 년 노벨 화학상 수상자
Quote about the second law of thermodynamics … joke
熱力學
熱 力
Thermodynamics – why we have to study ?
■ Thermodynamics
○ The word was coined around 1840 from two Greek root
• therme (heat) - as in thermometer
• dymanis (power) – as in dynamite
○ Thermodynamics deals with heat and dynamics (move-
ment)
■ Thermodynamics
○ A big progress was made in 19 th century
• Development of steams engine and trains
■ Thermodynamics was one of the most important
issue at that time
○ Transformation of heat to work
It seems like everything was already established – all problems are solved (?)
- Do we still need thermodynamic problems to study ?
Energy…
Comparison
Thermodynamics
Provides… Analysis
Assessment
열역학을 잘 이해한다면 유리한 점
■ 모든 분야의 기초가 되기 때문에 항상 유용한 학문이다 .
○ 화학 공정 분야 – 공정 설계의 기초 자료를 제공함 .
○ NT/IT 분야 - 새로운 물성을 지닌 소재 ( 나노 물질 / 전자재료 등 ) 의 분자간의 상호
작용을 설명하는 기초가 됨 .
○ 생물 분야 – 생물의 에너지 전환 , 단백질의 상호작용 등을 이해하는 기초가 됨 .
○ 에너지 분야 – 신재생 에너지 , 에너지 변환 , 에너지 저장
최근 가장 많은 주목을 받고 있는
탄소 중립 , 수소 경제 , CCSU
ESG 경영 , LCA 등의 개념과 가장 밀접한 관계가 있음 .
A best century for energy research
Thermodynamics provide
theoretical background for assessment
Introduction
에너지는 없다 ~!
11
Introduction
■ Everyday life is closely related to the quantities
called heat and work.
Do we know the exact meanings/implications
for heat/work and energy ?
12
Heat/Work=Energy ?
13
열에 대한 이상한 표현
14
분석 결과
15
열에 대한 올바른 표현
16
Heat ? – reason for confusions…
• When hot body is in contact with cold body,
something flows
• Only to one direction
• Hot to cold (O)
• Cold to hot (X)
• Until Joule’s experiment, heat was not con-
sidered as a transit of energy
• No connection with energy
• Unit of Heat Phlogiston ?
• Calorie Caloric ?
• British Thermal Unit (BTU) Heat ?
Energy ?
• Joule
17
Heat ?
■ Phlogiston theory
The phlogiston theory (from the Ancient Greek φλογιστόν phlogistón "burning
up", from φλόξ phlóx "flame"), first stated in 1667 by Johann Joachim Becher, is
an obsolete scientific theory that postulated the existence of a fire-like element
called "phlogiston", which was contained within combustible bodies and re-
leased during combustion. The theory was an attempt to explain processes of
burning such as combustion and the rusting of metals, which are now collec-
tively known as oxidation.
Caloric theory
Antoine Lavoisier developed the explanation of combustion in terms of oxygen in
the 1770s. In his paper "Réflexions sur le phlogistique" (1783), Lavoisier argued
that phlogiston theory was inconsistent with his experimental results, and pro-
posed a 'subtle fluid' called caloric as the substance of heat. According to this
theory, the quantity of this substance is constant throughout the universe, and it
flows from warmer to colder bodies. Indeed, Lavoisier was one of the first to use
a calorimeter to measure the heat changes during chemical reaction.
18
Calorimetry
■ Energy measurement : calorimeter
○ A Bomb calorimeter
○ Boyle, Lavoisier and Laplace used
calorimeter to measure heat given off by a
live guinea pig.
○ Respiration is a kind of combustion
■ Nowadays it is common to measure heat
given off by food using calorimeter for
planning diet.
19
Work ?
Work is performed when force acts through distance
W Fdl
Force ?
– Newton’s Second Law of Motion
– F = ma /gc
kg m / s 2 g cm / s 2 lbm ft / s 2
g c 1 1 32.174
N dyne lb f
gc: conversion constant
20
Work ?
Work accomplished by change in volume of a system
– Work is done when pressure is exerted from surroundings
– Sign convention
• Work is done to the system (+) : Volume shrinks (-)
• Work is done by the system (-) : Volume expands (+)
P
p F / A P2
dW pAd (V t / A) pdV t
V2t
W t pdV t
V1
P1 V
V2 V1
21
Amount of work depend on the path !
p p p
p1 p1 p1
p2 p2 p2
V V V
V1 V2 V1 V2 V1 V2
22
Energy …
■ The word energy derives from the Greek ἐνέργεια en-
ergeia, which possibly appears for the first time in the
work of Aristotle in the 4th century BCE.
■ The concept of energy emerged out of the idea of vis
viva (living force), which Gottfried Leibniz defined as
the product of the mass of an object and its velocity
squared; he believed that total vis viva was conserved
■ In 1807, Thomas Young was possibly the first to use the
term "energy" instead of vis viva, in its modern sense
23
Energy
• Galileo (1584) and Isaac Newton (1642-1726)
• Established General Principle of Conservation of Energy
• Ability to work (Energy) is conserved.
2
mu
• Kinetic Energy EK
2gc
• Potential Energy
mzg
EP
gc
24
Energy
• Energy Conservation
E K E P 0
mu22 mu12 mz2 g mz1 g
0
2 gc 2gc gc gc
• Energy conservation for pure mechanical processes
• During the period of development of the law, heat was not generally rec-
ognized as a form of energy
• Heat was considered an indestructible fluid called caloric
• No connection was made between heat resulting from friction
• The law was limited in application to frictionless mechanical processes
25
Joule’s Experiments
• James P. Joule (1818-1889)
• First experiment to understand the heat and its relation to work and energy
(1840)
• Amount of work and temperature changes of the fluid were measured
• Proved that there is a close relationship between heat and energy
• Heat is a form of energy tranfer
26
Energy, Heat and Work
■ Dictionary Definition of Energy
○ “Ability to work”
■ Difference between Heat/Work and Energy
○ Heat and Work
• Accompany changes
• Transfer of energy
에너지는 추상적 개념이다 (Abstraction)
에너지는 상태 함수이고 , 일과 열은 경로 함수이다 .
일과 열은 우리가 실제로 경험하는 에너지 이동 현상이다 .
27
The First Law of Thermodynamics
• Difference between “Energy” and “Heat/Work”
• Energy
• Can be stored
• Abstract quantity
• Forms : Internal / Potential / Kinetic
• Heat and Work
• Energy in transit across the boundary
• Measurable quantity
• Never contained in the body or system
28
Internal Energy
• What happened to the energy added to the fluid as work ?
• Contained in another form internal energy
• Internal Energy
• Do not include the energy due to macroscopic position or movement
energy of molecules internal to the substance
• Molecules possess due to ceaseless motion
• Kinetic energy of translation
• Kinetic energy of rotation
• Kinetic energy of vibration
• Internal energy have exact definition
• Cannot be measured directly
• Only changes are measured and used
29
Heat / Work and Energy
Energy State 1 (U1)
Heat
Change !
Work
Energy State 2 (U2)
Heat/Work 는 change 가 있는 경우에만 발생한다 .
Energy 는 state variable 이다 .
Heat/work 는 path function 이다 .
Heat/work 는 system boundary 를 통하여 전달되는 에너지 입출을 의미함 .
30
Virtual Experiment
https://phet.colorado.edu/en/simulation/ener
gy-forms-and-changes
31
Virtual Experiment 1
32
The First Law of Thermodynamics
- System and Surroundings
Although energy assumes many forms, the total quantity
of energy is constant, and when energy disappears in one
form it appears simultaneously in other forms.
Surroundings Everything with which the system interacts
System The region in which the process occurs
(Energy of the system) (Energy of Surroundin gs) 0
33
Energy Balance for Closed Systems
• “Closed System”
X No transfer of matter between system and surroundings
Closed System
Transfer of matter is allowed
Open System
34
Quote about the law of thermodynamics…
만일 당신이 알기 원한다면 , 모든 자연현상을 지배하는 단 하나의 사실이 있다는 것을 알 수 있다 .
이 법칙은 우리가 아는 한 예외가 전혀 없다 .
이 법칙은 에너지 보존법칙이라고 불린다 .
이 법칙은 에너지라고 일컫는 어떤 양이 존재함을 이야기하고 있는데 , 형태가 여러 가지로 변하더라도 전체 양이 변하지
않는다 .
이 법칙은 수학적으로 표현되는 가장 추상적인 개념이다 .
이 법칙은 어떤 일이 일어나더라도 변하지 않는 수학적인 양이 존재함을 의미한다 . 이 법칙은 어떤 메커니즘이나 기반이
든든한 이론을 의미하지 않는다 .
이 법칙은 자연이 어떤 속임수를 부리는지 몰라도 모든 일이 끝나고 나서 우리가 숫자를 계산하고 나면 그 값이 같다는
이상한 사실을 말한다 .
Robert Feynman
1965 년 노벨 화학상 수상자
35
The First Law of Thermodynamics
36
Energy Balance for Closed Systems
• EnergyEBalance
(Energy orEquation
surroundin gs) Q W
• Convention for W and Q
• When there is
E (Energy oran increase
surroundin gs)inenergy
Q W then sign is +
E (Energy or the system ) Q W
Closed system
No kinetic and potential energy change
U t Q W dU t Q W
37
Intensive and Extensive Properties
• Types of Properties
• Extensive Properties : Depends on system size
n,m, Vt = nV, Ut = nU, ….
• Intensive Properties : Does not depend on system size
T, P, V, U
Although Vt and Ut for a homogeneous system of arbitrary size are exten-
sive properties, specific and molar volume V and specific and molar inter-
nal energy U are intensive
38
The First Law of Thermodynamics
For n = 1 U Q W dU Q W
• Property Relation : connects U to measurable properties
• U : immeasurable
• Q and W : measurable
• No absolute value for U
• The relation provide means to calculate changes in U
There exists a form of energy, known as internal energy U, which is an in-
trinsic property of a system, functionally related to the measurable coor-
dinates which characterize the system. For a closed system, not in motion,
the changes in property are given by above equation.
39
Thermodynamic State and State Function
• State Functions and Path Functions
• State functions (properties)
• The value itself does not depend on the past history of substances nor means.
• Only depends on present condition, however reached
• VChanges are represented by difference
U1 of two values
1
dV VSpecific
• VExample)
2
2 V1
Volume U
V (V) or density,
2
U 2 U
dU Internal 1 U
Energy
• Path function (properties)
• Value depend on the nature of the process causing the change
• Represented as area rather than a point
Q Q
• Example ) Heat and Work W W
40
Thermodynamic State and State Function
• Example of state function and path function
• 서울에서 부산 까지 가는데 소요되는 총거리 : Path Function
• 어느 고속도로를 택하느냐에 따라 달라짐
• 서울에서 부산까지 직선 거리 : State Function p
• History 에 무관함 .
p2
• Graphical Representation
• Path Function : Area (Work)
• State Function : Point (p and V)
p1 V
V2 V1
41
Notation of Other Books
• For some books, thedUfirst
dQ law of thermodynamics is written
dW
as; Work is + sign when system does work.
This type of sign convention is not recommended by
IUPAC (International Union of Pure and Applied Chemistry)
• To discriminate state function and path function,
dU Q W
42
Virtual Experiment 2
43
Equilibrium
• “Equilibrium”
• Static condition : Absence of change
• Absence of any tendency toward change on macroscopic scale
• Changes are caused by driving forces
• Imbalance in mechanical forces : energy transfer as work
• Temperature difference : energy transfer as heat
• Gradient in chemical potential : transfer of substance from one
phase to another
44
The Reversible Process
A process is reversible when its direction can be reversed at
any point by an infinitesimal change in external conditions
45
Reversible Expansion of a Gas
• Imaginary Piston / Cylinder Assembly
Surroundings = Frictionless Piston
Evacuated Space No heat loss
Equilibrium
pressure balances
weight of piston and
all it supports
Effect of gravity on
molecules are small
No heat transfer
from cylinder
46
Irreversible Process
oscillation of piston
viscous nature of gas
molecules into
chaotic motion
dissipative process
cannot be reversed
47
Reversible Process
• Imaginary process – free
of dissipative effects
• Mass – infinitesimal (in-
finitely small)
• Process can be reversed
forward and backward
48
Reversible Process
• Is frictionless
• Is never more than differentially removed from equilibrium
• Traverses a succession of equilibrium states
• Is driven by forces whose imbalance is differential in magnitude
• Can be reversed at any point by differential change in external condi-
tions
• When reversed, retraces its forward path, and restores initial state of
system and surroundings
49
The Ideal Gas
• No interaction between molecules (B/V, C/V2 ,…=0)
Z 1 or pV RT Ideal gas
• Internal energy (U) of gases
• Real gas : function of T and p
• Ideal gas : function of T only
• Pressure dependency resulting from intermolecular force
• There is no dependency in p
• The Equation of State Z 1 or pV RT
• Internal Energy U U (T )
50
Implied Property Relations for an Ideal Gas
dU dU
volume is a function of temperature only
• Heat capacity
Cv at const.
Cv (T )
dT V dT
Ua
Halso
• Enthalpy is pV U
function of RT H (Tonly
temperature )
dH dH
C P at const.
• Heat capacity pressure
C Pis(Ta)function of temperature only
dT P dT
dH d (U pV ) d (U RT )
• Heat Capacity
CP Relationship
CV R
dT dT dT
51
Equations for Process Calculation for Ideal Gases
• From the first
dU law
CV dT of
Q thermodynamics
W Q pdV
RT / V
• Combinepideal gas law CP CV R
dV dV T, V
Q CV dT RT W RT
V V
dp dp T, p
Q CP dT RT dW RdT RT
p p
C C W pdV p,V
Q V Vdp P pdV
R R
52
Equations for Process Calculation for Ideal Gases
- (1) Isothermal Process
dU CV dT Q W Q PdV U 0
dH CP dT Q Ws H 0
Q W
T= const.
V2 p
Q RT ln RT ln 2
V1 p1
V2 p2
W RT ln RT ln
V1 p1
DO NOT try to memorize the equation !
Memorize the sequences of derivation !
53
Equations for Process Calculation for Ideal Gases
- (2) Isobaric Process
dU CV dT Q W Q pdV U CV dT
dH CP dT Q Ws H C P dT
H Q
P= const.
Q H C P dT
dV
W RT
V
dp
W RdT RT W R (T2 T1 )
p
W pdV
54
Equations for Process Calculation for Ideal Gases
- (3) Isochoric Process
dU CV dT Q W Q pdV U CV dT
dH CP dT Q Ws H C P dT
U Q
V= const.
Q U CV dT
dV
W RT
V
dp
W RdT RT W 0
p
W PdV
55
Equations for Process Calculation for Ideal Gases
- (4) Adiabatic Process
dU CV dT Q W Q pdV U CV dT
dH CP dT Q Ws H C P dT
Q 0
dQ=0
R / CV
dV dT R dV integration T2 V1
Q CV dT RT 0
V T CV V T1 V2
R / CP
dp dT R dp integration T2 p
Q CP dT RT 0 2
p T CP p T1 p1
CP / CV
C C dp C dV p2 V1
Q V Vdp P pdV 0 P integration
R R p CV V p1 V2
56
Equations for Process Calculation for Ideal Gases
- (4) Adiabatic Process
R / CV ( C P CV ) / CV
T2 V1 T2 V1
TV 1 const .
T1 V2 T1 V2
R / CP
T2 P2 T2 p2
( CP CV )/ CP
Tp (1 )/ const.
T1 P1 T1 p1
CP / CV
p2 V1
pV const.
p1 V2
C P / CV These equations are restricted
to const. heat capacities and
reversible, adiabatic processes
Q 0
W CV dT CV T
57
Equations for Process Calculation for Ideal Gases
- (4) Adiabatic Process
• Other expression for WORK calculation
W CV dT CV T
R
CV
1
RT
W CV T
1
Use p instead of T1 or T2
( 1)/ ( 1)/
R(T2 T1 ) p1V1 p2 RT1 p2
W CV T 1 1
1 1 p1 1 p1
58
Equations for Process Calculation for Ideal Gases
- (4) Adiabatic Process
• Values of Cp/Cv
• Monatomic gases : 1.67 (He, Ne, Kr,…)
• Diatomic gases : 1.4 (H2, N2, O2, …)
• Simple polyatomic gases : 1.3 (CO2, SO2, NH3, CH4,…)
59
Equations for Process Calculation for Ideal Gases
- (5) Polytropic Process
• Polytropic : “Turning many ways”
pV const.
0 p const isobaric
1 pV RT const isothermal
pV const adiabatic
V const isochoric
p 0
Can be used to represent a
1 in-between processes
V
60
Equations for Process Calculation for Ideal Gases
- (5) Polytropic Process
• Using ideal gas equation,
pV const. TV 1 const .
p RT / V Tp ( 1)/ const.
( 1)/
RT1 p2
W pdV 1
1 p1
( 1)/
( ) p2
Q 1
( 1)( 1) p1
constant heat capacity
61
Irreversible Processes
• Equations in (1)-(5)
• Only valid for mechanically reversible, closed system for
ideal gases
• Properties changes (dU, dH) are also same regardless of
the process State Properties
• Heat and Work amount depends on the nature of
process (reversible/irreversible, closed/open) Path
function
• For irreversible processes, the following procedures are
commonly employed
W is determined Efficiency (h)
For reversible process is multiplied
62
