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Chemical Engineering

Thermodynamics

Yang, Yanhui

Content

• Reversibility

– Irreversible and reversible processes

• Entropy

– Joule’s experiment, ideal Carnot cycle, analysis of Carnot cycle,

efficiency, concept of entropy, entropy calculation

• 2 nd law of thermodynamics

– 2 nd law, entropy balance for open system, ideal work and lost

work.

• 3 rd law of thermodynamics

2

Reversibility

• Irreversible processes: changes in the system which cannot be

reversed in their entirety without making changes elsewhere in the

universe.

• Reversible processes: a process is reversible if a second process

can be performed such that surroundings and the system can be

restored to their initial state except for infinitesimal changes.

• We will illustrate the characteristics of reversible processes by way

of an example:

• Expansion of a piston-cylinder arrangement with mass m placed on

the piston and ideal gas in piston.

• We choose the system as the gas.

3

Reversibility

• The work done is:

• However, during the expansion, we don’t know how changed and

W cannot be calculated this way.

• Work can be calculated by measuring the effect of this process on

the surroundings.

• Do a force balance on the system (path 1):

• Solving for and substituting into

we get

4

Reversibility

• For simplicity, let’s take

and

. We conclude

and

.

• The work required to bring the system and the surroundings back to

their initial state is

.

• When m is moved onto the platform, the gas expands irreversibility

against

. Both the system and surroundings cannot be brought

back to their original state without expenditure of work. An external

agent must lift m to

.

5

Reversibility

• Consider the same expansion in two steps (path 2):

6

Reversibility

is greater than

. More work is done by the

gas in path 2 than in path 1.

.

is less than

.

• Note also that in each case, the difference between the external

force and gas pressure is finite during the expansion, e.g., during 1 st

step, it starts out at

expansion.

and expands.

for 2 nd

7

Reversibility

• Is there a path for which we do not need to do work to put the

system and the surroundings into their original state? If yes, what

are the characteristics of such a path?

• Yes, a reversible path (path 3). System traverses equilibrium states.

• Consider dividing m into N with N platforms and dividing the

expansion process into N steps.

8

Reversibility

, work for isothermal reversible

expansion.

• Work to reverse:

. As

. Both system and the surroundings can be brought

back to their initial state without expenditure of work

∆

• During the expansion at each step:

. As

9

Entropy

• Consider Joule’s experiments:

• In Joule’s experiments, mechanical work is converted to internal

energy and temperature of the system rises.

• Note however that we never observe the paddles to start turning to

raise the weight with temperature of the water decreasing, even

though first law is valid for both processes.

• There is a missing law. There is a natural order of the states of the

systems such that it is impossible for some states to proceed others

within an adiabatic enclosure. This is called adiabatic accessibility.

10

Entropy

• Ideal Carnot cycle: idealized reversible engine cycle operating in a

completely reversible manner in a 4-step cycle

11

Entropy

• Analysis of the ideal Carnot cycle

• System: n kmol of an ideal gas in a cylinder-piston assembly.

• Process: a 4-step cyclic processes (all reversible)

• Step 1-2: isothermal and reversible heat absorption at T1 (T1=T2=TH)

• Amount of heat absorbed by the system (the working fluid):

• Step 2-3: adiabatic and reversible gas expansion from T2 to T3

12

Entropy

• Step 3-4: isothermal and reversible heat rejection at T3 (T3=T4=TC)

• Amount of heat rejection by the system (the working fluid)

• Step 4-1: adiabatic and reversible gas compression from T3 to T1

13

Entropy

•

For a cyclic process:

•

Efficiency is defined as ratio of net work done over heat absorbed:

•

14

Entropy

• Carnot efficiency:

• As QH is positive and QC is negative, a negative sign needs to be

inserted when absolute-value signs are removed.

• There exists a property (Q/T) whose change in a cyclic process is

given by

15

Entropy

• We already have postulated the existence of a state function S(U, X)

that determines whether state B is adiabatically accessible from

state A. We postulate that S is monotonically increasing function of

U.

,

, “thermodynamics temperature” the scale of

this temperature turns out to be the same as the ideal gas

temperature scale.

• Expanding S in its independent variables:

,

• For a reversible process:

, F is the property of

system, such as pressure (P).

,

16

Entropy

,

• For an adiabatic reversible process, dS=0 and dQrev=0.

=0

,

• But all these quantities are state functions, so this equality holds

even for non-adiabatic processes as well. it should be always zero.

• Substituting definition of T,

we get:

17

Entropy

• Simplify the derivation

,

• In the previous derivation: is generalized force,

is the

generalized displacement. They are replaced by –PdV (PV work)

18

Entropy calculation

• Entropy changes without phase change:

• Isobaric heating:

• Isothermal process:

• Isometric heating:

• Entropy changes involving phase change:

19

Entropy calculation

• Example: calculate the changes in entropy when 100 kg of liquid

water is heated from 50 °C and 1 bar to 230 °C and 28 bar.

• System: 100 kg of liquid water originally at 50 °C and 1 bar

• Process: heating from 50 °C and 1 bar to 230 °C and 28 bar

• Solution:

P

• Assumption:

230 °C, 28 bar

• From Steam table:

• 100*( 2.6099-0.7037)=190.62kJ/K

50 °C, 1 bar

230 °C, 1 bar

T

20

21

2 nd law of thermodynamics

• All processes proceed in a direction such that the total entropy

change is positive, approaching zero as the process approaches

reversibility

• Isolated systems maximize their entropy. Note that 2 nd law applies

only to isolated systems. Practically, we can always apply 2 nd law to

the universe since universe is an isolated system.

• The total entropy of the universe is ever increasing.

• Inequality holds for all real processes. Equality is a limiting case of

idealized reversible processes.

22

2 nd law of thermodynamics

•

Carnot cycle:

•

Heat transfer between two reservoirs at TH and Tc insulated from

other parts of the universe:

•

System: cold reservoir

•

Process: heat transfer

•

Entropy change of cold reservoir:

•

Entropy change of hot reservoir:

•

23

2 nd law of thermodynamics

•

Example: An inventor has devised a complicated non-flow process

in which 1 kmol of air is the working fluid. The net effects of the

process are claimed to be as follows:

– A change in state of the air from 500 K and 2 bar to 350 K and 1 bar

– The production of 2,000 kJ of work

– The transfer of an undisclosed amount of heat to a reservoir at 300 K

•

Determine whether the claimed performance of the process is consistent

with the 2 nd law. Assume that air is an ideal gas for which CP=7R/2 and

CV=5R/2.

•

Solutions:

•

•

24

2 nd law of thermodynamics

• Air changes from 2 bar and 500 K to 1 bar and 350 K

• Heat transfer to the cold reservoir at 300 K, from 1 st law:

• Entropy change of the gas (system)

25

2 nd law of thermodynamics

• Entropy balance for open systems:

• Rate of entropy generation: based on 2 nd law of thermodynamics:

26

2 nd law of thermodynamics

• Rate of total entropy change of the system:

• Rate of change of entropy of the surroundings:

• 2 nd law:

• When entropy generation is zero (

), process is internally

reversible within the CV

• Heat transfer between the CV and its surroundings must also be

reversible.

• Steady state entropy balance:

• Rate of entropy accumulation:

27

2 nd law of thermodynamics

• Ideal work: for a completely reversible process under steady-state

flow condition, rate of entropy generation:

• With one entering and one leaving streams and one Q term:

• From steady state energy balance (1 st law, neglecting kinetic energy

and potential energy):

fs

• Thermodynamics efficiency:

28

2 nd law of thermodynamics

• Lost work: wasted work due to irreversibility in a process (steady-

state flow process, expressed in terms of rates):

• From steady-state energy balance:

fs

• For a single surroundings temperature:

• Divided by flow rate:

• The greater the irreversibility of a process, the greater the rate of

entropy generation and the greater the amount of energy wasted

29

3 rd law of thermodynamics

• The entropy of all perfect crystalline substances at 0 K is zero:

• A more general form of the third law applies to systems such as

glasses that may have more than one minimum energy state: the

entropy of a system approaches a constant value as the

temperature approaches zero.

• It is impossible by any procedure, no matter how idealized, to

reduce the temperature of any system to zero temperature in a finite

number of operations.

30

Revisit Carnot cycle

(1 st law of thermodynamics)

, cyclic process, S is state function

(2 nd law of thermodynamics)

,

(not all the heat can be converted to work)

(3 rd law of thermodynamics)

31

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