# SECOND LAW OF THERMODYNAMICS

For any process we have First Law which states Q – W = ΔE. 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=ΔE.

Q

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 .

Q

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.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 . Qin BOILER WORK IN TURBINE WORK OUT PUMP CONDENSOR Qout Here QNET = Qin – Qout = WNET = Wout .

Another such cycle is the jet engine Cool air Compressor Combustion Chamber Turbine Hot gases Work given to compressor Fuel flow to C. But when they are combined together they form a closed system as no mass enters or leaves the system. CONDENSOR AND PUMP.C Shaft Work from Turbine The working fluid does not have the same properties as the inlet after the end of process. Now performance of a Heat Engine is determined by it’s ability to reduce this Qout as mush as possible. In a Heat Engine Qout is the energy which is not utilized and is rejected. 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. 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. All are open systems and do not operate in a cycle individually. . THERMAL EFFICIENCY We now look at some means of determining the performance of Heat Engines. But Qout is necessary to get a cycle . Here also the cycle is not achieved. TURBINE . so our effort is to minimize it. 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 ηTh = WNet Qin − Qout Q = = 1 − out Qin Qin Qin Thus the higher the value of Qout the lower the value of ηTh 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 ηTh = 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 now see a few examples. We still need to have it to have a proper cycle.

KELVIN-PLANCK STATEMENT IT IS IMPOSSIBLE FOR ANY DEVICE THAT OPERATES IN A CYCLE . WNet . It also implies that NO HEAT ENGINE CAN HAVE EFFICIENCY OF 1 This shall be seen later. There are two ways of expressing the Second Law . Here however some heat is lost in the pipes so the heater’s efficiency is defined as Efficiency = Heat given to Water Energy given by heater . 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.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. we will at this moment express it in relation to Heat Engines. 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. We know now For Heat Engines ηth = A. Converts Electrical Work into Heat. Let us see other devices Qin Water Heater.

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. Air at Room Temp. The amount of Heat produced by the fuel depends upon the Heating Value of Fuel. Combustion Chamber HHV or LHV One kg of Fuel at Room Temp. This has a high value because Heat is given off as H 2O condenses. E. Lower Heating Value of Fuel. So now the combustion efficiency is defined as – ηCombustion = C. 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 = . Combustion efficiency.(LHV) when H2O in the products is in vapor state. 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.B. A combustion device converts Chemical energy into heat energy. D.

but it is possible to develop a device which can do this by specific means.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 η Overall = ( η Comb ) X ( ηTh ) X ( ηGenerator )    ÷  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. So lets look at a device which also operates in a cycle but operates in a manner totally opposite to the Heat Engine . Now this cannot be done naturally . What if we want to transfer heat from low temperature to a high temperature. 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.

Let’s 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 4 QL Heat removed from Low Temperature The processes are a. c. this goes through a cycle and can be shown to be reverse cycle of a Heat Engine as .High Temperature Reservoir QH Device QL Low Temperature Reservoir Win If the device is required to give heat to High Temperature Device (QH) . d. (4-1)Compression to High Pressure vapor. then it is called HEAT PUMP If the device is required to remove heat from Low Temperature Device (QL) . b. Condenser. (3-4)Isothermal Change of phase from Liquid to Vapor Compressor. (2-3)Pressure reduction to give Low pressure and Low Temperature Refrigerant Evaporator. Expansion valve. then it is called REFRIGERATOR In fact a refrigeration process is a combination of four components which operate together as a cycle. ( 1-2)Change of phase from compressed vapor to compressed liquid.

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. 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).412 BTU Watt Hour of electrical energy consumed so if COP = 1 then EER = ( 3. Air Conditioners and refrigerators are also evaluated by another index called as ENERGY EFFICIENCY RATING. An A/C can be used as a Heat Pump if we reverse it. (EER) where EER = QL ( In BTU ' s ) now 1Wh = 3.QH If QH is important then we call it Heat Pump.412 ) COPRef .

And supposing the heat engine violates the second law . AND PRODUCES NO EFFECT OTHER THAN THE TRANSFER OF HEAT FROM A LOW TEMPERATURE BODY TO A HIGH TEMPERATURE BODY. Also generally EER and COP of refrigerators decrease with decreasing TL. other than heat. The reverse requires input of Work QH QL Low TEMPERATURE RESERVOIR Both Statements of Second Law govern the conversion of energies. Supposing we have a combination of Heat Engine and Refrigerator operating between the same two reservoirs. High TEMPERATURE RESERVOIR To do this we need to put energy into the cyclic device . So freezers have Low COP. The statement is IT IS IMPOSSIBLE TO CONSTRUCT A DEVICE THAT OPERATES IN A CYCLE . It is only possible to transfer heat from HTR to LTR naturally. CLAUSIUS STATEMENT OF SECOND LAW This statement relates to Heat Pumps and Refrigerators. EQUIVALENCE OF TWO STATEMENTS Both Statements are equivalent and either of them can be used to express the Implications of Second Law.Most A/C’s have EER of 8-12.

Read Pages 271-273 . 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 .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. 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.

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

g. but they are the standard to which we compare the real processes in nature. If a body moves in one direction. a part of the kinetic energy is converted into heat by friction. b. so as to reduce irreversibility but we cannot eliminate friction.They can be several. Lets investigate the factors which cause irreversibilities. We try to reduce friction as much as possible . Sometimes we even need friction to do some work. A car moves because of friction between the tires and road surface. The heat generated goes into the surrounding. and does not occur in nature . . The reverse path depends upon the degree of irreversibility present in the process. When we walk it is friction which allows us to do so. 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. Here ΔENET will more be 0 You must understand that REVERSIBLE PROCESS is an ideal concept . hence to achieve better design and performance we need to lower the factors which cause irreversibilities. c. hence the process is irreversible because the heat cannot be taken back. f. d. Some of the major ones are :a. IRREVERSIBILITIES reduce the efficiency of devices . It is very difficult to walk on slippery surfaces.P A B 2 1 V The process goes from 1 to 2 and then comes back to original state by two different paths. e.

If we move the piston in slowly . the gas will fill the vacuum quickly. Gas Vacuum Membrane So to reverse the process we have to put work into system to compress the gas. and we will get less PdV is given to the system. 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 . Now if we move the piston outwards in a fast manner . then pressure at piston face reduces very fast . and more work has to be done to move the piston. Frictionless Now if we have unrestrained expansion . A slow movement will give more work.UNRESTRAINED EXPANSION AND FAST COMPRESSION We have earlier seen the concept of QUASI-STATIC PROCESS. at the face of the piston. ( 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). This pressure wave will oppose movement . No work is given out of the system. and cause irreversibilities. . then that is also IRREVERSIBLE Now if the membrane is removed . a Compression wave is not set up and less work will be required to move the piston down.

then we need some external force to bring it back to its original shape. Heat will go from system to the surroundings. we will have an Irreversible Process. across a finite temperature difference. System at 5 oC Q 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 . + _ INELASTIC DEFORMATION Once the bar has deformed . heat is generated and goes to the surroundings.HEAT TRANSFER Whenever we have Heat Transfer . CHEMICAL REACTIONS REACTANTS A B PRODUCTS A+B To reverse and get A and B we have to get work from surroundings . ALL HEAT TRANSFER PROCESSES ARE IRREVERSIBLE ELECTRIC RESISTANCE WORK Q As the current flows through the wire . thus getting external work from the surroundings. We cannot put heat into the system and expect the wire to generate electricity. The result will be energy loss of the surroundings.

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. System with no irreversibility 2 P 1 V Now if a process is such that there may be irreversibility in the system . Here the forward path of the process is the same as the reverse path.INTERNALLY AND EXTERNALLY REVERSIBLE PROCESS A reversible process is an ideal conception. Inelastic deformation etc. Non quasi process. . friction. For such a process there is no heat transfer. It is the best process between two states. We generally call such a process a Reversible process. Now if a process is reversible then it is called INTERNALLY REVERSIBLE if there are no irreversibilities within the system. Chemical reaction .

CARNOT CYCLE A cycle which is totally made up of reversible processes. d. but it is the best cycle possible.called as CARNOT CYCLE. c. b. We will now look at a special cycle which is totally reversible . St 3 to 4 QOUT is Zero 1 4 Reversible Adiabatic Compression St 4 to 1 P 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 . 1 2 Reversible Isothermal Expansion. 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. is called a Reversible Cycle . A Carnot cycle involves four processes. 4 3 Reversible Isothermal Compression. St 1 to 2 Qin is Zero 2 3 Reversible Adiabatic Expansion St 2 to 3 H E A T S I N K TL is QL Const. This is an ideal concept . a.

REVERSED CARNOT CYCLE Since a Carnot Cycle is made up of 4 Reversible processes . . so it can be reversed. This can also be achieved by both open and closed systems. And we have P 1 TH TL Q=0 2 4 T 1 QH 4 Q= 0 2 3 V WNet QL 3 V This cycle is called a REVERSED CARNOT CYCLE. QH at TH 1 BOILER 2 Q2-3 is zero TURBINE PUMP Q4-1 is zero 4 QL at TL CONDENSOR 3 Such a cycle whether closed or open is called a CARNOT HEAT ENGINE because it produces work from heat input.This cycle can also be done in an open system as long as we have the four essential processes.

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

VIOLATION OF KELVIN-PLANCK STATEMENT .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.

Then WA > WB and QL < QL A B 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 . Both have same QH but ηA > ηB . and so we get HIGH TEMPERATURE RESERVOIR QH = 0 WA-WB QLB − QLA LOW TEMPERATURE RESERVOIR This again becomes a violation of Second Law .Further we can also show that two reversible engines will have the same efficiency when operating between the same to Reservoirs.

HIGH TEMPERATURE RESERVOIR at TH QH WA REV A QL for A LOW TEMPERATURE RESERVOIR at TL QH REV B WB QL for B η A = QH −QL QH For and A η 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. We then define the Thermodynamic scale in such a way that QH φ ( TH ) = where QH and QL are functions of a scale QL φ ( TL ) We define the scale as such that QH TH = where TH and TL are defined as per new scale QL TL .THERMODYNAMIC TEMPERATURE SCALE Most of our Temperature scales are based on some property of a substance like thermal expansion. Now the efficiencies of each engine will be the same because they operate between the same reservoirs. 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.

16 The magnitude of oK is defined as between absolute Zero and Triple point of Water.This scale is known as Kelvin Scale and temperatures are known Absolute Temperatures.16 1 of the temperature interval 273.00 QL TL = 0 QH TH Now this is not possible so Absolute Zero is not achievable. Now an Irreversible Engine cannot be better than a Reversible engine operating between the same temperature limits . Scale QH TH So the highest efficiency which can be achieved by a Carnot Heat engine is governed by TL and TH. 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 ηTh = 1 − L = 1 − L = 1. and this allows us to determine which IRR engine is better. 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 ηth = 1 − QL T = 1 − L if we use Absolute Temp. Lets say we have . The relation between celcius and absolute scale is given by o K = o C + 273.

25 Q η= 1− Q B 900 = 1− = 0.6 = 60% So the engine is fairly close to 40 %. So if we have an engine operating between 750 oK and 300 oK the carnot efficiency will be 0. Source( Limited by Material Strength) Lowest possible temp Sink ( Limited by the cooling medium) .75 = 0.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 η A Carnot T = 1− L TH L H L = 1− 0. FOR A CARNOT ENGINE η 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.225 800 Q η= 1− Q H Engine B is the better Engine So if we have engines operating between two temperature limits then if its TL TH η 1− th = η 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 η 1− th > Most engines have an efficiency below 40 %.10 1000 620 = 1− = 0.

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.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 . Also read pages 291-294 .