│化工熱力學│ 導讀版

Introduction to Chemical
Engineering Thermodynamics
Seventh Edition

J. M. Smith, H. C. Van Ness, M. M. Abbott ◎ 著

楊肇政 ◎ 審閱
Chapter 5
The Second Law of
Thermodynamics
Copyright © the McGraw-Hill Companies, Inc. Permission required for reproduction or display.
熱力學第一定律是能量守恆,並未告知process朝哪方向進行,並且單
位heat和單位work是等值的,但實際上,

1.work可以可以完全轉換成其他能量及其他work, 且efficiency 100%.

2.heat轉換轉換成work (or mechanical, electrical energy),其

efficiency 常常不超過40 %.

3.兩物體間的heat transfer 是由高溫傳到低溫.

The second law of thermodynamics包含

1. 在cyclic process, system 是不可能將所吸收的heat 完全轉換成

system 對外界做work.
2. No process is possible which consists only in transfer heat from
low temperature to high temperature.
Heat engine包含下列4個步驟

1.室溫的liquid water用pump 打入boiler使liquid water壓力成高壓

2.boiler提供heat使liquid water變成high temperature的steam

3. High temperature steam進入turbine對turbine做shaft work,而其變

成low temperature low pressure steam.

4.由turbine出口出口的steam放熱給surroundings而自己凝結成liquid.
再用pump打入boiler,完成1個cycle.

簡單說heat engine cylce, system在高溫吸收熱量|𝑄𝐻 | from 熱源 ,

在低溫放出熱量|Q C |給冷源,並對外界做功 |W|.
5.2 HEAT ENGINES 熱機 P161

|𝑄𝐶 |>0所以<1證明證明熱力學第二定律statement 1, reversible

process 可提高. A heat engine operating in a completely
reversible is called a Carnot engine.
Carnot cycle

1. A system at Tc undergoes a reversible adiabatic process to rise

temperature to 𝑇𝐻 (temperature of hot reservoir).
2. The system contacting with hot reservoir at 𝑇𝐻 undergoes a
reversible isothermal process to absorb |𝑄𝐻 |from hot reservoir.
3. The system undergoes a reversible adiabatic process that brings
the temperature back to 𝑇𝐶 (temperature of cold reservoir).
4. The system contacting with cold reservoir at 𝑇𝐶 undergoes a
reversible isothermal process to reject |𝑄𝐶 |to clod reservoir and
returns to its initial state.
Carnot Theorem

1. For two given heat reservoirs no engine have a thermal

efficiency higher than that of a Carnot engine . (Fig. 1)

2. The thermal efficiency of a Carnot engine depends on the

temperature level and not upon the working substance of the
engine.
則對hot reservoir 是由低溫傳熱給高溫,違反熱力學第二定律
statement 2,所以heat engine E之thermal efficiency 小於 Carnot
engine C之thermal efficiency.
5.3 THERMODYNAMIC TEMPERATURE SCALES 熱力學溫標 P163
5.3 THERMODYNAMIC TEMPERATURE SCALES 熱力學溫標 P164
5.3 THERMODYNAMIC TEMPERATURE SCALES 熱力學溫標 P165
5.3 THERMODYNAMIC TEMPERATURE SCALES 熱力學溫標 P165
(5.8)式跟(5.5)式比較(T)=T因此因此蓋氏temperature (based on
ideal gas) is a thermodynamic scale, independent the substance.

|𝑊| 𝑇𝐶
= = 1-
|𝑄𝐻 | 𝑇𝐻

當𝑇𝐻 →∞ or 𝑇𝐶 →0, 則→1

5.3 THERMODYNAMIC TEMPERATURE SCALES 熱力學溫標 P166
5.4 ENTROPY 熵 P167

雖然應用於reversible Carnot cycle但亦可應用於其他

reversible cycle.
對任一reversible cycle 可看
成很多reversible Carnot
cycle組合,對任一Carnot
cycle 可寫成
5.4 ENTROPY 熵 P168

𝑑Q𝑟𝑒𝑣
是property (因為‫ׯ‬ = 0表示independent of path)
𝑇

S: entropy
5.4 ENTROPY 熵 P169

𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑟𝑒𝑣 𝑑𝑄𝑟𝑒𝑣 𝑑Q𝑟𝑒𝑣

‫= 𝑇 ׯ‬0=‫𝑇 𝐵𝐷𝐴׬‬ +‫׬‬BCA
𝑇
= ‫𝑇 𝐵𝐷𝐴׬‬ -‫𝐵𝐶𝐴׬‬
𝑇

𝑑𝑄𝑟𝑒𝑣 𝑑Q𝑟𝑒𝑣
∆𝑆 𝑡 =
‫𝑇 𝐵𝐶𝐴׬‬ = ‫𝑇 𝐵𝐷𝐴׬‬ =𝑆𝐵𝑡 -𝑆𝐴𝑡
If a process is reversible adiabatic,𝑑𝑆 𝑡 = 0, then the process is isentropic.

Any system undergoes a finite reversible process then

𝑑Q𝑟𝑒𝑣
∆𝑆 𝑡 = ‫𝑇 ׬‬ (5.13)

When a system undergoes an irreversible process between two

equilibrium states, 設計一個reversible process使其initial, final state跟實
際發生的state相同再利用(5.13)式計算∆S 𝑡 (S是是state function
independent of path)

若system純粹只是heat transfer不管是reversible or irreversible則

𝑡 𝑑𝑄
∆S =‫׬‬
𝑇
不過若irreversible process其driving force is pressure則system

𝑑Q𝑟𝑒𝑣
∆𝑆 𝑡 =‫׬‬
𝑇
5.5 ENTROPY CHANGES OF AN IDEAL GAS 理想氣體的熵變化 P170
Unit mole or mass fluid 進行mechanical reversible process in
a closed system
雖然雖然(5.14)是由ideal gas undergoes mechanical reversible
process,但(5.14)只跟system property有關因此(5.14)可用來計算
ideal gas 之entropy change不管是reversible or irreversible均可.
5.5 ENTROPY CHANGES OF AN IDEAL GAS 理想氣體的熵變化 P171
5.5 ENTROPY CHANGES OF AN IDEAL GAS 理想氣體的熵變化 P171
5.6 MATHEMATICAL STATEMENT OF THE SECOND LAW P173

Consider two heat reservoirs, one at 𝑇𝐻 and second at lower

temperature 𝑇𝐶 . Let heat |Q|be tranferred from the hot
reservoir to the cooler reservoir.

當𝑇𝐻 -𝑇𝐶 變小則∆S𝑡𝑜𝑡𝑎𝑙 變小, 當𝑇𝐻 只比𝑇𝐶 稍微高一點點則∆S𝑡𝑜𝑡𝑎𝑙 →0,

heat transfer is reversible. 所以irreversible heat transfer
∆S𝑡𝑜𝑡𝑎𝑙 >0, reversible heat transfer ∆S𝑡𝑜𝑡𝑎𝑙 = 0.
Consider an irreversible adiabatic process (A→B) in a closed
system

若fluid 由state B reversible 回復到state A, 包含包含1. reversible

adiabatic compression to the initial pressure. 2. reversible constant
pressure 使其回復到initial volume.
5.6 MATHEMATICAL STATEMENT OF THE SECOND LAW P174

由B→A

𝑖𝑟𝑟𝑒𝑣 𝑟𝑒𝑣
若考慮A B 𝐴 𝑝𝑟𝑜𝑐𝑒𝑠𝑠 ∆𝑈 = 0 因此

由second law statement 1知所吸收 heat不能完全轉換成work

所以上式𝑄𝑟𝑒𝑣 < 0,𝑆𝐴𝑡 < 𝑆𝐵𝑡 . For irreversible adiabatic A→ B
∆𝑆𝑠𝑢𝑟 =0, ∆𝑆𝑡𝑜𝑡𝑎𝑙 (A→ B)=∆𝑆𝑠𝑦𝑠 + ∆𝑆𝑠𝑢𝑟 =𝑆𝐵𝑡 -𝑆𝐴𝑡 >0
Consider a cyclic heat engine that takes in heat |𝑄𝐻 |from reservoir
at 𝑇𝐻 and discards heat |𝑄𝐶 | to another reservoir at Tc

∆𝑆𝑡𝑜𝑡𝑎𝑙 =∆𝑆𝑠𝑦𝑠 +∆𝑆𝑠𝑢𝑟 =∆𝑆𝑠𝑢𝑟 =

5.6 MATHEMATICAL STATEMENT OF THE SECOND LAW P175
HW 5-10 An ideal gas CP=3.5 R, is heated in a steady-flow heat exchanger
from 343.15 K to 463.15 K by another stream of the same ideal gas which
enters at 593.15 K. Th e flow rates of the two streams are the same,
and heat losses from the exchanger are negligible. (a) Calculate the
molar entropy changes of the two gas streams for both parallel and
countercurrent flow in the exchanger. (b) what is ∆Stotal in each case?
HW 5-19 An ideal gas, C P=3.5 R, CV=2.5 R undergoes a cycle consisting
of the following mechanically reversible steps.
(a) An adiabatic compression from P 1, V1, T1 to P2, V2, T2
(b) An isobaric expansion from P 2, V2, T2 to P3 (=P2), V3, T3
(c) An adiabatic expansion from P3, V3, T3 to P4, V4, T4
(d) An constant-volume process from P 4, V4, T4 to P1, V1 (=V4), T1
If T 1=473.15 K, T 2=773.15 K, T 3=1973.15 K, T 4=973.15 K determine the
thermal efficiency.
HW 5-17 A Carnot engine operates between temperature levels of 600 K
and 300 K. It derives a Carnot refrigerator, which provides cooling at
250 K and discards heat at 300 K. Determine a numerical value for the
ratio of heat extracted by the refrigerator ( “cooling load ”) to the heat
delivered to the engine (“heating load”).
HW 5-21 1 mole of an ideal gas C P=3.5 R, C V=2.5 R is compressed
adiabatically in a piston/cylinder device from 2 bar and 298.15 K to 7
bar. The process is irreversible and requires 35 % more work than
reversible adiabatic compression from the same i nitial state to the
same final pressure. What is the entropy change of the gas?
HW 5-26 1 mole of an ideal gas is compressed isothermally but
irreversible at 403.15 K from 2.5 bar to 6.5 bar in a piston/cylinder
device. The work required is 3 0 % greater than the work of reversible,
isothermal compression. The heat transferred from the gas during
compression flows to a heat reservoir at 298.15 K. Calculate the
entropy changes of the gas, the heat reservoir, and total.
5.7 ENTROPY BALANCE FOR OPEN SYSTEMS 開放系統的熵平衡 P176
5.7 ENTROPY BALANCE FOR OPEN SYSTEMS 開放系統的熵平衡 P177
5.7 ENTROPY BALANCE FOR OPEN SYSTEMS 開放系統的熵平衡 P177
5.7 ENTROPY BALANCE FOR OPEN SYSTEMS 開放系統的熵平衡 P178
5.7 ENTROPY BALANCE FOR OPEN SYSTEMS 開放系統的熵平衡 P178
P179
5.8 CALCULATION OF IDEAL WORK 理想功的計算 P181
5.8 CALCULATION OF IDEAL WORK 理想功的計算 P182
5.8 CALCULATION OF IDEAL WORK 理想功的計算 P184
5.9 LOST WORK 損失功 P185
5.9 LOST WORK 損失功 P185
5.9 LOST WORK 損失功 P186
5.9 LOST WORK 損失功 P186
5.10 THE THIRD LAW OF THERMODYNAMICS 熱力學第三定律 P188

The third law of thermodynamics

The absolute entropy is “0” for all perfect crystalline substance at 0 K.

HW 5-33 A refrigeration system cools a brine from 298.15 K to 258 .15 K
qt the rate of 20 Kg/sec. Heat is discarded to the atmosphere at a
temperature of 303.15 K. What is the power requirement if the
thermodynamic efficiency of the system is 0.27? The specific heat of
the brine is 3.5 KJ/Kg-K
HW 5-39 A steady-flow adiabatic turbine accepts gas at 500 K, 6 bar
and discharges at 371 K, 1.2 bar. Assuming ideal gases, determine
(per mole of gas) W, Wideal, Wlost and SG. ( =300 K)