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SECOND LAW OF THERMODYNAMICS

For any process we have First Law which states Q W = E. Now every process has to satisfy this Law. However satisfying the First Law does not mean that it will actually happen. Let us look at this aspect:Q

A current flows through a resistor and gives Heat. It satisfies Q - W=E.

Now supposing we have a wire and we give heat to it. Now this will not cause a current to flow. Although it may possibly satisfy the first Law if it was possible.

Supposing we have a paddle wheel in a closed system. If we rotate the paddle wheel the air is agitated and gets heated up. Heat comes out of system. First law
Q

is found to be satisfied What now if we put Heat into the system . This will not cause Paddle to rotate .

We thus find that processes occur in a certain direction , and it may not be possible to reverse the process. The aspect of Process is governed by the Second Law. A PROCESS CAN ONLY TAKE PLACE IF IT SATISFIES THE FIRST AND SECOND LAW . THE SECOND LAW WILL INTRODUCE US TO A NEW PROPERTY ENTROPY

Before we formulate the second law we need to clear few concepts. THERMAL ENERGY RESERVOIRS These are Bodies or Systems , which have large thermal energies. THESE CAN ABSORB OR SUPPLY LARGE ANMOUNTS OF HEAT WITHOUT ANY TEMPERATURE CHANGE WITHIN THEIR SYSTEM. Examples are
ATMOSPHERE SEA CAN ABSORB LARGE AMOUNT OF HEAT TRANSFER WITHOUT ANY TEMPERATURE CHANGE.

Industrial Furnace Sun

CAN SUPPLY A LOT OF HEAT WITHOUT ANY TEMPERATURE CHANGE.

A Thermal Reservoir which absorbs a large amount of heat is called a HEAT SINK A Thermal Reservoir which SUPPLIES a large amount of heat is called a HEAT SOURCE We now look at the concept of Heat Engines We had seen earlier that it is possible to convert one form of energy to another form. It is possible to convert Work into Heat : Friction It is however with difficulty that we are able to convert Heat into Work. We can do so by using specialized devices called as HEAT ENGINES. HEAT ENGINES a. b. c. d. Receive heat from a High Temperature Source Convert part of Heat into work Reject part of Heat to a Low temperature Sink Operate in a cycle.

We thus represent the Heat Engine in the following manner.

Qin

Work

Heat Engines usually have a fluid from which heat either taken or removed during the cyclic process. This is called the WORKING FLUID

Qout

The best example of a Heat Engine is a Steam Power Plant.


Qin BOILER WORK IN TURBINE WORK OUT

PUMP

CONDENSOR Qout

Here QNET = Qin Qout = WNET = Wout - Win Sometimes we use the term Heat Engine for devices which do not operate in Thermodynamic cycle. For example a petrol engine
Cool air and fuel Work to Flywheel Combustion in cylinder Hot gases in exhaust The working fluid does not have the same properties as the inlet after the end of process

Another such cycle is the jet engine


Cool air Compressor Combustion Chamber Turbine Hot gases

Work given to compressor

Fuel flow to C.C

Shaft Work from Turbine

The working fluid does not have the same properties as the inlet after the end of process. Here also the cycle is not achieved.

In fact all devices which use internal combustion are not satisfying the strict definition of Heat engines The Steam Power plant has four individual components ie BOILER, TURBINE , CONDENSOR AND PUMP. All are open systems and do not operate in a cycle individually. But when they are combined together they form a closed system as no mass enters or leaves the system. So for a closed system which operates in a cycle

QNET =WNET

or

Qin Qout =Wout Win


For a Heat Engine WNet is a very important commodity. THERMAL EFFICIENCY We now look at some means of determining the performance of Heat Engines. In a Heat Engine Qout is the energy which is not utilized and is rejected. But Qout is necessary to get a cycle , so our effort is to minimize it. Now performance of a Heat Engine is determined by its ability to reduce this Qout as mush as possible. So THERMAL EFFRICIENCY is very much related to the quantity of Heat rejected.

In general terms the performance of any system is given by

Performance =

Desired Actual Output Re quired Input Net Work out WNet = Heat put in Qin

For Heat Engines Performance Criteria is Thermal Efficiency

Thermal Efficiency =

or

Th =

WNet Qin Qout Q = = 1 out Qin Qin Qin

Thus the higher the value of Qout the lower the value of Th generally for cyclic engines Qin=QH and HEAT FLOW FROM HIGH TEMP RESERVOIR TO CYCLE Qout = QL HEAT FLOW FROM CYCLE TO LOW TEMP RESERVOIR

Th =

WNet Q = 1 L Qin QH

Thermal Efficiency is always less than 1. it is equal to 25 to 30 % it is equal to 45 50 %

For IC Automobile Engines using Petrol For Diesel engines Gas Turbine and Steam Power Plants

it is equal to 30 35 %

Our effort is to keep QL as low as possible. We still need to have it to have a proper cycle. We now see a few examples.

SECOND LAW OF THERMODYNAMICS We have now understood the concept of Energy Reservoirs and Heat Engines We will now try to understand the Second Law by using these concepts. There are two ways of expressing the Second Law , we will at this moment express it in relation to Heat Engines. KELVIN-PLANCK STATEMENT IT IS IMPOSSIBLE FOR ANY DEVICE THAT OPERATES IN A CYCLE , TO RECEIVE HEAT FROM A SINGLE RESERVOIR AND PRODUCE NET AMOUNT OF WORK This can be represented as
QH Work This implies that it is absolutely mandatory for any Heat engine to reject heat. It also implies that NO HEAT ENGINE CAN HAVE EFFICIENCY OF 1 This shall be seen later. NOT POSSIBLE

Since efficiency is paramount for devices which convert one form of energy to another so we will now look at some other devices which do so. We know now

For Heat Engines th =


A.

WNet . Let us see other devices Qin

Water Heater. Converts Electrical Work into Heat. Here however some heat is lost in the pipes so the heaters efficiency is defined as

Efficiency =

Heat given to Water Energy given by heater

B.

Combustion efficiency. A combustion device converts Chemical energy into heat energy. The amount of Heat produced by the fuel depends upon the Heating Value of Fuel, which is defined as Amount of Heat released when unit mass of fuel is completely burnt at Room Temperature and the products are then cooled to Room Temperature Now this definition can be represented as
Combustion products at Room Temp. Air at Room Temp. Combustion Chamber HHV or LHV One kg of Fuel at Room Temp.

Generally Room Temperature is taken as 25 oC

We have two values of Heating Value of Fuel Higher Heating Value of Fuel.(HHV) when H2O in the products is in liquid state. This has a high value because Heat is given off as H 2O condenses. Lower Heating Value of Fuel.(LHV) when H2O in the products is in vapor state. So now the combustion efficiency is defined as

Combustion =
C. D. E.

Heat Released Heating Value


Electrical Power Output Mechanical Power Input

Generator Efficiency = Motor Efficiency =

Mechanical Power Output Electrical Power Input Amount of Light given in LUMENS Amount of Energy consumed in WATTS

Lighting Efficiency =

Sometimes we have several devices linked together so we define what is termed as Overall Efficiency = Product of individual efficiencies So if we have the following arrangement
Fuel and Air Electrical Work

QH Heat Engine Work

Combustion Chamber

Generator

QL

Overall = ( Comb

) X ( Th ) X ( Generator )

Q Q W QH e H L = X X * QH QL QH HHV m Fuel We = * HHV m Fuel


We will now look at two other energy conversion devices which is used a lot in our environment. These are referred to as REFRIGERATORS AND HEAT PUMPS. REFRIGERATORS AND HEAT PUMPS Now we do understand that heat flows high temperatures to low temperatures naturally. What if we want to transfer heat from low temperature to a high temperature. Now this cannot be done naturally , but it is possible to develop a device which can do this by specific means. So lets look at a device which also operates in a cycle but operates in a manner totally opposite to the Heat Engine

High Temperature Reservoir QH Device QL Low Temperature Reservoir Win

If the device is required to give heat to High Temperature Device (QH) , then it is called HEAT PUMP

If the device is required to remove heat from Low Temperature Device (QL) , then it is called REFRIGERATOR

In fact a refrigeration process is a combination of four components which operate together as a cycle. Lets look at one
800 Kpa 30 oC 2 Condensor 1 QH Heat Given to High Temperature 800 Kpa 60 oC COMPRESSOR SHAFT WORK IN

EXPANSION VALVE

120 Kpa -25 oC 3

Evaporator

120 Kpa -25 oC

QL Heat removed from Low Temperature

The processes are a. b. c. d. Condenser. ( 1-2)Change of phase from compressed vapor to compressed liquid. Expansion valve. (2-3)Pressure reduction to give Low pressure and Low Temperature Refrigerant Evaporator. (3-4)Isothermal Change of phase from Liquid to Vapor Compressor. (4-1)Compression to High Pressure vapor.

this goes through a cycle and can be shown to be reverse cycle of a Heat Engine as

QH

If QH is important then we call it Heat Pump. Work

QL

If QL is important then we call it Refrigerator

CO-EFFICIENT OF PERFORMANCE The performance of Refrigerators and heat pumps is assessed by an index called as Co-efficient of Performance (COP). This is defined as COP = Desired output Re quired input so COPRef = QL QL 1 = = QH Win QH QL 1 QL

COPHP =

QH QH 1 = = Win QH QL 1 QH QL

COP can be greater than 1 depending upon the value of W in

Now COPHP = so

QH W

and

COPRef =

QL W

COPHP COPRef =

QH QL = 1 for the same device W

Air Conditioners are also a type of refrigerator where the Low Temperature is a room or a building. An A/C can be used as a Heat Pump if we reverse it. Air Conditioners and refrigerators are also evaluated by another index called as ENERGY EFFICIENCY RATING. (EER) where

EER =

QL ( In BTU ' s ) now 1Wh = 3.412 BTU Watt Hour of electrical energy consumed

so if COP = 1 then EER = ( 3.412 ) COPRef

Most A/Cs have EER of 8-12.

Also generally EER and COP of

refrigerators decrease with decreasing TL. So freezers have Low COP. CLAUSIUS STATEMENT OF SECOND LAW This statement relates to Heat Pumps and Refrigerators. The statement is IT IS IMPOSSIBLE TO CONSTRUCT A DEVICE THAT OPERATES IN A CYCLE , AND PRODUCES NO EFFECT OTHER THAN THE TRANSFER OF HEAT FROM A LOW TEMPERATURE BODY TO A HIGH TEMPERATURE BODY.
High TEMPERATURE RESERVOIR To do this we need to put energy into the cyclic device , other than heat. It is only possible to transfer heat from HTR to LTR naturally. The reverse requires input of Work

QH

QL Low TEMPERATURE RESERVOIR

Both Statements of Second Law govern the conversion of energies. EQUIVALENCE OF TWO STATEMENTS Both Statements are equivalent and either of them can be used to express the Implications of Second Law. Supposing we have a combination of Heat Engine and Refrigerator operating between the same two reservoirs. And supposing the heat engine violates the second law

High TEMPERATURE RESERVOIR

( QH + QL ) Work = QH

QH Heat Engine Violates the Second Law

QL Low TEMPERATURE RESERVOIR

The combination will look like this


High TEMPERATURE RESERVOIR QL The combination is a violation of the Clausius Statement. THUS A VIOLATION OF K-P STATEMENT IS A VIOLATION OF CLAUSIUS STATEMENT and Vice Versa

QL Low TEMPERATURE RESERVOIR

We had first evolved the PMM1 from First law . And now we have PMM2 from Second law
PMM1 W QH W PMM2

A device which behaves like PMM1 or PMM2 is not possible Any device must satisfy First and Second Laws completely. Read Pages 271-273

REVERSIBLE AND IRREVERSIBLE PROCESSES Second Law states that no Heat Engine can have 100 % efficiency. Well if this is not possible , then what could be the highest efficiency which can be achieved. To answer this we need to study the concept of REVERSIBLE and IRREVERSIBLE Processes. Lets look at a few process;a. Cooling of water. The water will lose heat to air. We cannot force the heat to go back to the water. In fact we will have to use some energy source to heat the water back. b. Stopping of a car by applying the brakes. When we apply brakes , the friction generated by the brake pads cause the car to stop. In the process the brakes get heated. Now we cannot apply heat to cold brakes and expect the wheel to rotate. We will have to apply some other energy source to rotate the wheel. Now this means that to reverse the process some external energy has to be put in. This energy has to come from surroundings. So what could be a reversible process. Lets first define it. REVERSIBLE PROCESS IS A PROCESS THAT CAN BE REVERSED WITHOUT LEAVING ANY TRACE ON THE SURROUNDINGS. This is only possible, if the process retraces its path when the process reverses.
P 2 Because the process goes from 1 to 2 and then reverses along the same path to go from 2-1, so ENET = 0 V

Ein 1

Eout

An irreversible process on the other hand will not reverse along the same path to reach its original state , and hence will require energy or give energy to come back to its original state. Here ENET is not equal to 0 These will be shown as

1 V

The process goes from 1 to 2 and then comes back to original state by two different paths. The reverse path depends upon the degree of irreversibility present in the process. Here ENET will more be 0

You must understand that REVERSIBLE PROCESS is an ideal concept , and does not occur in nature , but they are the standard to which we compare the real processes in nature. IRREVERSIBILITIES reduce the efficiency of devices , hence to achieve better design and performance we need to lower the factors which cause irreversibilities. Lets investigate the factors which cause irreversibilities.They can be several. Some of the major ones are :a. b. c. d. e. f. g. FRICTION UNRESTRAINED EXPANSION OR COMPRESSION MIXING OF TWO GASES HEAT TRANSFER ACROSS A FINITE TEMPERATURE DIFFERENCE ELECTRICAL RESISTANCE INELASTIC DEFORMATION CHEMICAL REACTIONS

FRICTION occurs when bodies are in motion. If a body moves in one direction, a part of the kinetic energy is converted into heat by friction. The heat generated goes into the surrounding; hence the process is irreversible because the heat cannot be taken back. We try to reduce friction as much as possible , so as to reduce irreversibility but we cannot eliminate friction. Sometimes we even need friction to do some work. When we walk it is friction which allows us to do so. It is very difficult to walk on slippery surfaces. A car moves because of friction between the tires and road surface.

UNRESTRAINED EXPANSION AND FAST COMPRESSION We have earlier seen the concept of QUASI-STATIC PROCESS. ( A process which is so slow that property change is uniform in the system) Lets look at a Piston-Cylinder arrangement
Very Slow Frictionless movement of Piston inwards will keep the properties uniform Very Fast Frictionless movement of Piston inwards will cause a pressure buildup ( Compression Wave), at the face of the piston. This pressure wave will oppose movement , and more work has to be done to move the piston. If we move the piston in slowly , a Compression wave is not set up and less work will be required to move the piston down. Now if we move the piston outwards in a fast manner , then pressure at piston face reduces very fast , and we will get less PdV is given to the system. A slow movement will give more work.

Frictionless

Now if we have unrestrained expansion , then that is also IRREVERSIBLE


Now if the membrane is removed , the gas will fill the vacuum quickly. No work is given out of the system.

Gas

Vacuum

Membrane

So to reverse the process we have to put work into system to compress the gas.

FAST PROCESSES ARE HIGHLY IRREVERSIBLE SLOW PROCESSES ARE LESS IRREVERSIBLE However because of human nature to do processes in short time we tend to do most processes fast , and cause irreversibilities.

HEAT TRANSFER Whenever we have Heat Transfer , across a finite temperature difference, we will have an Irreversible Process.
Heat will go from system to the surroundings. System at 5 oC

Surrounding at 25 oC

Surrounding at 25 oC

QH

System at 5 oC

Refrigerator

QL

Work

If we want to reverse the process then we will have to refrigerate , thus getting external work from the surroundings. The result will be energy loss of the surroundings.

ALL HEAT TRANSFER PROCESSES ARE IRREVERSIBLE ELECTRIC RESISTANCE WORK

As the current flows through the wire , heat is generated and goes to the surroundings. We cannot put heat into the system and expect the wire to generate electricity.

INELASTIC DEFORMATION Once the bar has deformed , then we need some external force to bring it back to its original shape.

CHEMICAL REACTIONS
REACTANTS A B PRODUCTS A+B

To reverse and get A and B we have to get work from surroundings

INTERNALLY AND EXTERNALLY REVERSIBLE PROCESS A reversible process is an ideal conception. It is the best process between two states. Now if a process is reversible then it is called INTERNALLY REVERSIBLE if there are no irreversibilities within the system. Here the forward path of the process is the same as the reverse path.

System with no irreversibility

2 P 1 V

Now if a process is such that there may be irreversibility in the system , but there will be no irreversibility outside the system then this process is called EXTERNALLY REVERSIBLE
System with irreversibility

No irreversibility in the surroundings

Such is possible when Heat Transfer between system and surrounding is at same temperature

A TOTALLY REVERSIBLE PROCESS IS ONE WHICH HAS NO IRREVERSIBILITY EITHER IN THE SYSTEM OR IN THE SURROUNDINGS. We generally call such a process a Reversible process. For such a process there is no heat transfer, friction, Non quasi process, Chemical reaction , Inelastic deformation etc.

CARNOT CYCLE
A cycle which is totally made up of reversible processes, is called a Reversible Cycle . This is an ideal concept , but it is the best cycle possible. We will now look at a special cycle which is totally reversible ,called as CARNOT CYCLE. A Carnot cycle involves four processes, a. b. c. d. Reversible Isothermal Expansion Reversible Adiabatic Expansion Reversible Isothermal Compression Reversible Adiabatic Compression

If we use an ideal gas with a piston cylinder device then it is executed as


H E A T S O U R C E

QH

TH is
Const.

Reversible Isothermal Expansion. St 1 to 2

Qin is Zero

Reversible Adiabatic Expansion St 2 to 3

H E A T S I N K

TL is QL
Const.

Reversible Isothermal Compression. St 3 to 4

QOUT is Zero

Reversible Adiabatic Compression St 4 to 1

QH TH TL
2 T 1 2

Q=0
4

Q= 0
3 4 V

WNet QL
3 V

We can show it on P V as well as T V diagram

This cycle can also be done in an open system as long as we have the four essential processes.

QH at TH 1
BOILER

2 Q2-3 is zero
TURBINE

PUMP

Q4-1 is zero 4 QL at TL
CONDENSOR

Such a cycle whether closed or open is called a CARNOT HEAT ENGINE because it produces work from heat input. REVERSED CARNOT CYCLE Since a Carnot Cycle is made up of 4 Reversible processes , so it can be reversed. And we have
P 1

TH TL

Q=0
2

QH

Q= 0
2 3 V

WNet QL
3 V

This cycle is called a REVERSED CARNOT CYCLE. This can also be achieved by both open and closed systems.

THE CARNOT PRINCIPLES We have seen the KELVIN-PLANCK and CLAUSIUS STATEMENTS , as they govern Heat engines ,Refrigerators/Heat Pumps. We can now make two strong conclusions from these statements:A. The efficiency of an Irreversible Heat Engine is always less then the efficiency of a Reversible Heat Engine operating between the same two reservoirs. B. The efficiencies of all Reversible Heat Engines operating between the same two reservoirs are the same. THIS CAN BE PROVED BY SHOWING THAT THE VIOLATION OF EITHER STATEMENT IS VIOLATION OF SECOND LAW. Let us say that we have an IRR Heat Engine which has a higher efficiency than a REV heat engine. Both operate between the same reservoirs and take the same amount of QH ,
HIGH TEMPERATURE RESERVOIR QH (IRR) WIRR IRR QL (IRR) LOW TEMPERATURE RESERVOIR QH (REV) REV WREV

QL (REV)

Now if IRR > REV then WIRR > WREV and QLIRR < QLREV
Lets combine both the reversible and the Irreversible engines , but we reverse the Reversible Heat engine. And we take some work from the Irreversible engine and give it to Reversible engine

HIGH TEMPERATURE RESERVOIR QH (IRR) WIRR-WREV IRR QL (IRR) WREV QH (REV) REV QL (REV)

LOW TEMPERATURE RESERVOIR

This combination gives us

HIGH TEMPERATURE RESERVOIR QH = 0

WIRR-WREV

QL(IRR) QL (REV) LOW TEMPERATURE RESERVOIR

We have a device which is operating as a Heat Engine while exchanging with a single reservoir. VIOLATION OF KELVIN-PLANCK STATEMENT

Further we can also show that two reversible engines will have the same efficiency when operating between the same to Reservoirs. Both have same QH but

A > B . Then WA > WB and QL < QL


A

HIGH TEMPERATURE RESERVOIR QH WA REV A QL for A LOW TEMPERATURE RESERVOIR QH REV B WB

QL for B

We reverse B and combine both of them , and so we get

HIGH TEMPERATURE RESERVOIR QH = 0

WA-WB

QLB QLA
LOW TEMPERATURE RESERVOIR

This again becomes a violation of Second Law

THERMODYNAMIC TEMPERATURE SCALE Most of our Temperature scales are based on some property of a substance like thermal expansion. A THERMODYNAMIC TEMPERATURE SCALE IS INDEPENDENT OF THE PROPERTIES OF THE SUBSTANCE. Such a scale has been derived from the Carnot Principles ie The Second One The efficiencies of all Reversible Heat Engines operating between the same two reservoirs are the same.
HIGH TEMPERATURE RESERVOIR at TH QH WA REV A QL for A LOW TEMPERATURE RESERVOIR at TL QH REV B WB

QL for B

A =

QH QL QH For

and
A

B =

QH QL QH

For B

Here the efficiency is independent of the properties of the material used but is dependent upon the Heat transfer of each engine. Now the efficiencies of each engine will be the same because they operate between the same reservoirs. We then define the Thermodynamic scale in such a way that

QH ( TH ) = where QH and QL are functions of a scale QL ( TL )


We define the scale as such that

QH TH = where TH and TL are defined as per new scale QL TL

This scale is known as Kelvin Scale and temperatures are known Absolute Temperatures. The relation between celcius and absolute scale is given by
o

K = o C + 273.16
1 of the temperature interval 273.16

The magnitude of oK is defined as

between absolute Zero and Triple point of Water. A CONSTANT VOLUME IDEAL GAS THERMOMETER BEHAVES VERY CLOSELY WITH THE ABSOLUTE SCALE Now as per our definition absolute zero will be achieved when

QH TH Q T = which will mean Th = 1 L = 1 L = 1.00 QL TL = 0 QH TH


Now this is not possible so Absolute Zero is not achievable. We have come very close to it ie -260 oC We have defined the Carnot Heat Engine as a CARNOT HEAT ENGINE completely reversible cycle

Now th = 1

QL T = 1 L if we use Absolute Temp. Scale QH TH

So the highest efficiency which can be achieved by a Carnot Heat engine is governed by TL and TH. Now an Irreversible Engine cannot be better than a Reversible engine operating between the same temperature limits , and this allows us to determine which IRR engine is better. Lets say we have

HIGH TEMPERATURE RESERVOIR at TH = 400 oK WA = 100 W IRR A QL = 900W LOW TEMPERATURE RESERVOIR at TL = 300 oK QH = 1000 W QH = 800 W WB = 180 W IRR B QL =620 W

Now if there was a Carnot Engine operating between these temperatures then

Carnot

T = 1 L TH
L H L

= 1 0.75 = 0.25

Q = 1 Q
B

900 = 1 = 0.10 1000 620 = 1 = 0.225 800

Q = 1 Q

Engine B is the better Engine So if we have engines operating between two temperature limits then if its
TL TH

1 th = 1 th <

it is a reversible engine it is an irreversible engine it is an impossible engine

and if and if

TL TH TL TH

1 th >

Most engines have an efficiency below 40 %. So if we have an engine operating between 750 oK and 300 oK the carnot efficiency will be 0.6 = 60% So the engine is fairly close to 40 %. FOR A CARNOT ENGINE

TH

INCREASES IF TH INCREASES and also INCREASES IF TL DECREASES So we make an effort in Actual engines to have operation between Highest Possible temp. Source( Limited by Material Strength) Lowest possible temp Sink ( Limited by the cooling medium)

CARNOT REFRIGERATOR AND HEAT PUMP Based on our definition of Absolute Temperature we can say that

COPRe f =

QL QH 1 1 1 1 = = and COPH .P = = = T Q T QH QL QH QH QL 1 H 1 1 L 1 L QL TL QH TH

These are the highest COP of Refrigerator/heat Pump operating between two temperature limits . So we can say that

COPRe f =

1 TH 1 TL 1 TH 1 TL 1 TH 1 TL

Re versible refrigerator

COPRe f <

Irreversible refrigerator

COPRe f >

Not possible

COPHP =

1 Re versible Heat Pump TL 1 TH 1 Irreversible Heat Pump TL 1 TH 1 T 1 L TH Not Possible

COPHP <

COPHP >

Lets look at a few problems. Also read pages 291-294

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