Second Law of Thermodynamics: Motivation

ME 201 Spring 09

Gas

First Law: For a cycle

Thought Experiment: 1. Weight is lowered, turning the paddle Shaft work is done on the gas. 2. Then heat is transferred from the system to the surroundings completing the cycle.

Both

Q and W

are negative.

Question : With the given surroundings, (i.e. container, paddle wheel and weight) is the reverse cycle possible?
Second Law: Cycles 1

Second Law of Thermodynamics: Motivation

ME 201 Spring 09

High Temperature

Q
Low Temperature

Heat can be transferred from high temperature body to low temperature body.

Question : 1. Is the reverse possible? 2. How can we make it possible? Can you think of an example?

Second Law: Cycles

Heat Engine

ME 201 Spring 09

Gas Gas Gas Gas

TH

TC

Heat Engine: A device that operates in a thermodynamic cycle and does a

certain amount of net positive work through the transfer of heat from a high temperature body and to a low temperature body.
Second Law: Cycles 3

Heat Engine: Practical Example

ME 201 Spring 09

thermal

W (energy sought ) QH ( Energy that cos ts) QH QL QH 1 QL QH

Second Law: Cycles

Heat Pump: Practical Example

Heat Pump: A device that operates in a cycle, that requires work, and that

ME 201 Spring 09

accomplishes the objective of transferring heat from a low temperature body to a high temperature body.

QH
Condenser

Efficiency of a refrigerator is expressed as Coefficient of performance or COP:

Expansion Valve Evaporator

Compressor

QL ( Energy sought ) W ( Energy that cos ts) QL 1 QH QL QH 1 QL

QL

Refrigeration Cycle
Second Law: Cycles 5

The Kelvin-Planck Statement

ME 201 Spring 09

It is impossible to construct a device that will operate in a cycle and produce no effect other than the raising of a weight and the exchange of heat with a single reservoir.

Thermal Reservoir:
High Temperature A body to which and from which can be transferred indefinitely without change in the temperature of the reservoir. Note: Thermal reservoir always remains at a constant temperature. Example: Ocean, atmosphere

QH
W

IMPOSSIBLE

Second Law: Cycles

The Clausius Statement

ME 201 Spring 09

It is impossible to construct a device that will operate in a cycle and produce no effect other than the transfer of heat from a cooler body to a hotter body. High Temperature In effect it is impossible to construct a refrigerator that operates without an input of work.

QH

QL
Low Temperature

IMPOSSIBLE
Second Law: Cycles 7

Four Observations about the 2nd Law statements

1. Both statements of the second law are negative statements. Consequently they can not be directly proved. However every relevant experiment validates and non contradict the second law. 2. The two statements are equivalent. That is, truth of one implies truth of the other, or violation of one implies violation of the other. 3. Second Law implies the impossibility of constructing a perpetual motion machine (PMM) of the second kind.

ME 201 Spring 09

Note: PMM I would create work or energy out of nothing thus violating the First Law PMM II would extract heat from a source and then convert the heat completely into other forms of energy, thus violating the Second Law. PMM III would have no friction, and thus run indefinitely. But produce no work. 4. It is impossible to have a heat engine of 100% efficiency.
Second Law: Cycles 8

Next Question
If 100% efficiency is impossible, what is the maximum efficiency possible? To answer we need to talk about :

ME 201 Spring 09

Reversible and Irreversible Processes

A reversible process is one such that the system and all parts of the surroundings can be restored to their initial state. The effects of a reversible process can be undone such that there is no evidence of the process ever having occurred. Reversing a reversible process leaves no trace in either the system or the surroundings.

Second Law: Cycles

Factors that render processes irreversible

1. Friction -Q

ME 201 Spring 09

Incline 2. Unrestrained Expansion

Incline

Incline

Gas

Vacuum

Gas

3. Heat Transfer through a finite temperature difference

Second Law: Cycles

10

Factors that render processes irreversible

ME 201 Spring 09

4. Mixing of Two Different Substances

O2

N2

O2+N2

5. Hysteresis effects and the i2R losses encountered in electrical circuits 6. Ordinary combustion

Second Law: Cycles

11

The Carnot Cycle

High Temperature (TH)

ME 201 Spring 09

QH
Boiler

If 100% efficiency is impossible, what is the maximum efficiency possible for a thermodynamic cycle?
1. A reversible isothermal process in which heat is transferred from the high temperature reservoir. 2. A reversible adiabatic process in which the temperature of the working fluid decreases from high to low temperature. 3. A reversible isothermal process in which heat is transferred to the low temperature reservoir. 4. A reversible adiabatic process in which the temperature of the working fluid increases from low to high temperature.
12

Pump

turbine

Condenser

QL

Carnot Cycle

Low Temperature (TL)

Second Law: Cycles

Two Propositions regarding efficiency of a Carnot Cycle

First Proposition:

ME 201 Spring 09

It is impossible to construct an engine that operates between two given reservoirs and is more efficient than a reversible engine operating between the same two reservoirs.

Second Proposition:
All engines that operate on the Carnot Cycle between two given constant temperature reservoirs have the same efficiency.

Second Law: Cycles

13

The Thermodynamic Temperature Scale

The efficiency of a Carnot cycle is only dependent on the temperatures of the hot and cold reservoirs, hence
thermal

ME 201 Spring 09

QL QH

(TL , TH )
Lord Kelvin proposed
thermal

QL QH
(1)

TL TH

If we run the Carnot Cycle between the steam point and ice point (even though practically impossible), the thermal efficiency would be
thermal

Tice point Tsteam point

0.2680

If we wish to have the magnitude of the degree on the absolute scale to match the magnitude of the Celsius degree, we can write

Tsteam point Tice point

Solving (1) and (2),

100

(2) 273.15 K

Tsteam point

373.15 K and Tice point

Second Law: Cycles

It follows that T (C )

273.15 T ( K )
14

Example 1

ME 201 Spring 09

A heat pump heats a house in the winter. The interior temperature should be 20 0C. Heat transfer through the walls and ceiling are estimated to be 2400 kJ per hour per degree temperature difference between the inside and outside. a) If the winter outside temperature is 0 0C, what is the minimum power required to drive the heat pump?

QH

2400 (293.15 273.15)

48000 kJ / hour TAMB TAMB QL QH TROOM TROOM 44725 kJ / hour
QH QL 48000 44725 kJ / hour

TH=TROOM=293.15

QH

QL QH
W

QH

QL

QL
TL=TAMB=273.15

3275 kJ / hour

0.91 kW
15

Second Law: Cycles

Example 2
A Carnot heat engine receives heat from a high temperature reservoir at 527 C. the heat rejected from this engine is supplied to a second Carnot engine. This second engine rejects heat to a low temperature reservoir at 17 C. the first engine reject 400 kJ to the second engine. If both engines have the same efficiency, determine the following: The temperature of the high temperature reservoir for the second engine The energy received by the first engine from the 527 C source The work done by each engine The efficiency of each engine TA=800 K QA HE 1

ME 201 Spring 09

WA

QB = 400 kJ

TB
QB = 400 kJ HE 2 Q0 T0=290 K
16

a. Both engine have same efficiency, so

T 290 1 1 800 T

481 .6 K

WB

b. QA = QB (TA/TB) = 400 (800/481.6) = 664.45 kJ c. WA = QA-QB = 264.45 kJ WB = QB (1-T0/TB) = 159.136 kJ d. Efficiency = 1- 290/T = 0.3978
Second Law: Cycles

Summary
1. Motivation: 2nd Law gives direction in which processes and cycles can occur 2. Defined Heat Engine and Heat Pump/Refrigerator: since 2nd Law is stated in terms of them
HE

ME 201 Spring 09

W QH

QL 1 QH

HP

QH W

1 1 QL

REF

QH

QL W

1 QH QL 1

3. Stated the Kelvin Planck and Clausius forms of the 2nd Law 1. Proved that both these statements are equivalent. 2. It is impossible to have a heat engine of 100% efficiency. 4. Asked ourselves then what is the maximum possible efficiency? 1. Defined reversible and irreversible processes 2. Described one particular reversible cycle the Carnot Cycle. 3. Proved that a reversible cycle has the maximum efficiency, and all such reversible cycles have the same efficiency. 4. Argued that since the efficiencies of all reversible cycles are equal, the only parameter it depends on are TH and TL, i.e.
thermal

QL 1 QH

TL (TL , TH ) 1 TH

2nd Law for Processes: Inequality of Clausius

Q T 0

ME 201 Spring 09

High Temperature (TH)

QH
Boiler

Proof: 1. Consider a reversible Carnot cycle:

Pump

turbine

Wrev

Q T

QH TH

QL TL

2. Consider an irreversible cyclic heat engine

Condenser

QH
Carnot Cycle

QL

Wirr Wrev QL ,irr QH QL ,rev QL,irr QL,rev

QH TH QL ,irr TL 0
18

Low Temperature (TL)

Q T
Second Law: Processes

Entropy: A property of a system

P A 2

ME 201 Spring 09

Let a system undergo a reversible process from state 1 to state 2 along a path A, and let the cycle be completed along path B. Since cycle is reversible,

B
1

Q T

0
1

Q T

Q T

Now consider another reversible cycle, which proceeds first along path C, and then completed along path B. For this cycle,

Q T

0
1

Q T
2

Q T
2

Subtracting one from the other,

Q T

Q T

Second Law: Processes

19

Entropy: A property of a system

Since

ME 201 Spring 09

Q T

is the same for all reversible paths between state 1 and 2, conclusion

is that this quantity is independent of the path, and only depend on the end states, in other words, its a property. This property is called ENTROPY

dS

Q T S 2 S1

rev 2

Q T

rev

NOTE: Since entropy is a property, S 2 S1 is the same for all processes, both reversible and irreversible, between these two states. The above equation only enables us to find the change in entropy along a reversible path. However, once the change has been evaluated, this value is the magnitude of the entropy change for all processes between these two states.
Second Law: Processes 20

Entropy of a pure substance

ME 201 Spring 09

Values of specific entropy are given in thermodynamic tables in the same manner as specific volume and specific enthalpy. The corresponding unit is kJ/kg.K In the saturation region, the entropy may be calculated using the quality.

(1 x) s f

x sg

Second Law: Processes

21

Entropy change in a Reversible Process

TH
QH

ME 201 Spring 09

Let us consider a reversible Carnot Cycle 1. A reversible isothermal process in which heat is transferred from the high temperature reservoir. 2 2 2 Q 1 Q S 2 S1 Q 1 2 W turbine T rev TH 1 TH 1 2. A reversible adiabatic process in which the temperature of the working fluid decreases from high to low temperature. 3 Q 3 S3 S 2 0 T rev 2 3. A reversible isothermal process in which heat is transferred to the low temperature reservoir. 4 4 Q Q 1 S 4 S3 Q 3 4 2 T rev TL 3 TL 3 4. A reversible adiabatic process in which the temperature of the working fluid increases from low to high temperature. 3 1 Q S1 S 4 0 T rev 4 S
Second Law: Processes 22

1
Pump

Boiler

Condenser

QL

TL
T

1 W 4

QH QL

The Thermodynamic Property Relations

ME 201 Spring 09

Q dU W Q TdS and W
H U dH dH PV dU

PdV

TdS

dU

PdV

PdV

VdP

TdS VdP
For a unit mass

TdS

dH VdP

Tds Tds Td s Tds

du Pdv dh vdP du Pd v dh v dP
23

On a mole basis

Second Law: Processes

Entropy change in an Irreversible Process

P 2

ME 201 Spring 09

For 1

1,

Q T Q T

1 2

Q T Q T

2 1

Q T Q T

0
B

For 1
1

1,
2

0
B

v
Subtracting 2nd equation from 1st,

Q T

Q T
2

Since path A is reversible, and since entropy is a property,

2 2

Therefore,
1

dSC
1

Q T

Q T

dS A
A 1 1

dSC

As path C was arbitrary, in general, dS

Q T

Equality for a reversible process Inequality for an irreversible process 24

Second Law: Processes

Increase in entropy principle

In general,

ME 201 Spring 09

dS
Q

Q T
0
dSisolated
sys

For an isolated system,

dS sys

dS surr

Example 2: Suppose that 1 kg of saturated water vapor at 100 0C is condensed to a saturated liquid a 100 0C in a constant-pressure process by heat transfer to the surrounding air, which is at 25 0C. What is the net increase in entropy of the water plus surroundings? For the control mass (water) from the steam tables,

S c . m. ms fg 1 6.0480 6.0480 kJ / K Concerning the surroundings, we have Qto surroundin mhfg 1 2257.0 2257.0 kJ / K gs Q 2257 S surr 7.5700 kJ / K T0 298.15 Snet Sc.m. Ssurr 6.0480 7.5700 1.5220 kJ / K
Second Law: Processes 25

Lost work
For irreversible processes

ME 201 Spring 09

dS

Q T
S gen provided, S gen

dS

Q T

irr

Qirr
Again

TdS T S gen dU Wirr

TdS

dU
Wirr

PdV
PdV T S gen

Combining

This shows that the work is reduced by an amount proportional to the entropy generation. For this reason, the term T S gen is often called lost work, although it is not a real work or energy quantity lost, but a lost opportunity to extract work.

Second Law: Processes

26

Summary
1. Second Law of Thermodynamics

ME 201 Spring 09

2. Inequality of Clausius a) Equality holds for reversible processes b) Inequality holds for irreversible processes.

Q T

3. The property ENTROPY a) Equality holds for reversible processes b) Inequality holds for irreversible processes.

dS

Q T

4. Thermodynamic Property Relations:

5. Increase in Entropy 6. Lost Work

dS isolated
sys

Tds Tds

du Pdv dh vdP

Wirr

PdV T S gen
27

Second Law: Processes

Entropy change for an ideal gas

ME 201 Spring 09

Tds

du Pdv
du
and

Tds
For an ideal gas,

dh v dP
dh
and

For an ideal gas,

Therefore

cv0 dT P R T v

dT dv dT dP ds cv0 R ds c p0 Ru T v T P 2 2 dT v2 dT P2 s2 s1 cv 0 R ln s2 s1 c p0 Ru ln T v1 T P 1 1 1 T c p0 0 In ideal gas tables sT dT is listed. T P2 T0 0 0 s2 s1 sT2 sT1 Ru ln P 1

Second Law: Processes 28

Therefore

c p0 dT v Ru T P

Example 3

ME 201 Spring 09

Oxygen is heated from 300 to 1500 K. Assume that during this process the pressure dropped from 200 to 150 kPa. Calculate the change in entropy per kg. Use ideal gas tables and compare with result obtained by assuming constant specific heat value of c p 0 1.0714 kJ / kg K From ideal gas table, s2 s1

s2 s1
s2 s1

s2 s1
Using
2

P 1 150 (258.068 205.329) 8.3145 ln 200 55.131 kJ / kmol K 55.131 1.7228 kJ / kg K 32

P2 R ln P 1 1500 8.3145 150 1.0714 ln ln 300 32 200

sT02

sT01

Ru ln P2

c p 0 1.0714 kJ / kg K ,

s2 s1
1

c p0

dT T

1.7991 kJ / kg K
Second Law: Processes 29

Isentropic Efficiency

ME 201 Spring 09

For all the steady-flow devices we consider (such as turbines, compressors, pumps, and nozzles) the reversible adiabatic (isentropic) process is the standard to which real processes can be compared. Wact The isentropic efficiency is thus defined as isen

Wisen

Example 4 (Text Book Ex 7.7) Consider a steam turbine in which the steam enters as superheated vapor at 800 K and 6 Mpa and exits at 0.1 Mpa. The flow rate of the steam is 15 kg/s, and the isentropic efficiency of the turbine is 90%. Determine the outlet state of the steam and the power produced by the turbine.

Go through book solution

Second Law: Processes

30