Second law of thermodynamics Limitation of first law of thermodynamics

1. It states that during the cyclic change of closed system, net heat

transfer is equal to work transfer. The above condition does not indicates the flow of heat and work i.e. whether the heat flow from hot body to cold body or cold body to hot body. 2. It states that, heat and work are mutually convertible. Mechanical work can be fully converted into heat, but heat cannot be completely converted into work .this shows that heat and work are not fully convertible.

Second law of thermodynamics

It is defined in two ways

1. Kelvin Plank statement

It is impossible to construct a heat engine working on a cyclic process, whose sole aim is to convert heat energy supplied into an equivalent amount of work.

2. Clausis statement
It is impossible for machine (heat pump and refrigerator) to transfer heat from a body at low temperature to a body at high temperature without aid of external work.

Perpetual Motion machine of Kind (PMM- 2 ) The device in which total amount of heat energy supplied is converted into work is called PMM It violates Kelvin Plank statement. Its efficiency is 100 % as the total amount of heat supplied is converted into work.

Equivalence of Kelvin Plancks and Clausius statement

Though Kelvin- Plancks and Clausius statements for second law of thermodynamics seem to be different, but they are equivalent to each other. It can be proved; if it is shown that violation of one statement means the violation of other and vice versa.

Violation of Kelvin Planck statement

Consider a heat engine having 100% efficiency (i.e. PMM- ) i.e. violating Kelvin Plancks statement .Such a heat engine will convert heat energy supplied Q1 into an equivalent amount of work (W). Q1 =W This work done produced can be utilized to drive a heat pump which receives amount of heat Q2 from cold body (sink) and rejects an amount of heat ( Q1 + Q2) to hot body (thermal reservoir) as shown in figure.

If the combination of the heat engine and heat pump is considered as a single system ,the result will be a device (such as heat pump ) which delivers Q2 from cold body to hot body without having any external work done, thus violating Clausis statement. Hence violating of Kelvin Plancks statement implies violation of Clausis statement.
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COP
Co-efficient of performance is defined as the ratio of heat extracted or rejected to work input. Heat extracted or rejected COP = -------------------------------Work input

Important terminologies
1. Thermal Reservoir It is a large body of infinite heat capacity whose temperature remains constant, whatever amount of heat is added or rejected from it. Ex; atmosphere, sea etc Source: source is a reservoir in which heat is absorbed. Sink: Sink is a reservoir in which heat is rejected.

HEAT ENGINE
Heat engine is a device, which operates in a cycle, to which heat is transferred and work is produced. A simple flow diagram of heat engine is given below

(COP) engine = Output Input (COP) engine = WE Q1 (COP) engine = Q1 - Q2

Q1

(COP) engine = 1- Q2
Q1

Reversible Heat Engine

It is a device working in a thermodynamic cycle, which conveys heat from low temperature reservoir to a high temperature reservoir with the help of work input.
A simple flow diagram of reversible heat engine is given below

(COP) r engine = Output Input (COP) r engine = Q1 WE (COP) r engine = Q1

Q1 - Q2

HEAT PUMP
Heat pump is a thermodynamic system, which transfer heat from a low temperature body and gives out the same to high temperature body. A simple flow diagram of heat pump is given below

(COP) pump = Output Input (COP) pump = Q1 WE (COP) pump =

Q1 Q1- Q2

(COP) pump = Q1
Q1- Q2

Refrigerator
Refrigerator is a thermodynamic system, which absorbs heat from a low temperature body (space to be cooled) and transfer it to high temperature body (atmosphere). A simple flow diagram of refrigerator is given below

(COP) R = Output Input (COP) R = Q2 WE (COP) R =

Q2 Q1- Q2

(COP) R = Q2
Q 1 - Q2

RELATION BETWEEN (COP)p and (COP) R We know (COP) pump = (COP) R =

Q1 Q1- Q2 Q2 Q1- Q2 Q2 +1 Q1- Q2
=

(COP) R +1 = (COP) R +1

Q1 Q1- Q2

(COP) R +1

(COP)p

No Heat pump Refrigerator 1. Heat pump is a Refrigerator is a thermodynamic system, thermodynamic system, which transfer heat which absorbs heat from a from a low temperature low temperature body body and gives out the (space to be cooled) and same to high transfer it to high temperature body. temperature body (atmosphere). 2. it works between hot body 2. It works between cold body temperature and temperature and atmosphere. atmosphere

No Heat engine Heat engine is a device, 1.

which operates in a cycle, to which heat is transferred and work is produced.

Heat pump Heat pump is a thermodynamic system, which transfer heat from a low temperature body and gives out the same to high temperature body. Here work is supplied

2.

Here work is produced.

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Carnot cycle
Carnot cycle is an ideal cycle and all the process in this cycle is reversible. The efficiency of Carnot cycle is maximum efficiency and no other cycle will have efficiency more then Carnot cycle. It is not possible in actual practice because heat addition and rejection at constant temperature is a very slow process and this process can not be achieved in actual practice and all process in this cycle is reversible. The Carnot cycle can not be performed in actual practice because of the following reason 1. It is impossible to perform a Frictionless process. 2. It is impossible to transfer the heat without temperature gradient. 3. Isothermal process can be achieved only if the piston moves very slowly to allow transfer so that the temperature remains constant. Adiabatic process can be achieved only if the piston moves as fast as possible so that the heat transfer is negligible due to a very short time available. The isothermal process and adiabatic process takes place during the same stroke therefore the piston has to very slowly for a part of the stroke and it has to move very fast during the remaining stroke. The variation of the movement of the piston during the same stroke is not possible.

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Why Carnot cycle cannot be realized in practical?

1) In a Carnot cycle all the four processes are reversible but in actual practice there is no process is reversible. 2) It is impossible to perform a Frictionless process. It is not possible to avoid friction moving parts completely. 3) It is impossible to transfer the heat without temperature gradient. 4) There are two processes to be carried out during compression and expansion. For isothermal process the piston moves very slowly and for adiabatic process the piston moves as fast as possible. This speed variation during the same stroke of the piston is not possible.

ASSUMPTION MADE FOR DESCRIBING CARNOT CYCLE 1) The piston moving in the cylinder does not develop any friction during motion. 2) The walls of piston and cylinder are considered as perfect insulator of heat 3) The cylinder head is so arranged that it can be perfect heat conductor or perfect heat insulator. 4) The transfer of heat does not affect the temperature of source and sink. 5) Working medium is a perfect gas and has constant specific heat. 6) Compression and expansion are reversible.

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Carnot cycle consist of four processes

Process 1-2: Reversible isentropic compression process. Process 2-3: Reversible isothermal heat addition process. Process 3-4: Reversible isentropic expansion process. Process 4-1: Reversible isentropic expansion process.

Process 4-1: Reversible isothermal heat rejection process.

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Carnots theorem
Carnot's theorem, also called Carnot's rule is a principle which sets a limit on the maximum amount of efficiency any possible engine can obtain, which thus solely depends on the difference between the hot and cold temperature reservoirs. It states that of all engine operating between a given constant temperature source and a given constant temperature sink, none has a higher efficiency than a reversible engine

HEA and HEB are the two engines operating between thye given source at temperature T1 and the given sink at temperature T2 Let HEA be any heat engine and HEB be any reversible heat engine.

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We have to prove that the efficiency of HEB is more than HEA. Let us assume that A > B let the rate of working of the engine be such that Q1A =Q2B=Q1

Since

A > B
WA > WB Q1A Q1B

WA > WB

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Now let HEA be reversed.Since HEB is a reversible heat engine ,the magnitudes of heat and work transfer quantities will remain same ,but the direction will be revrsed ,as shown in the figure . Since WA > WB , some part of WA (Equal to WB ) may be fed to drive the reversed heat engine EHB. Since Q1A =Q2B=Q1 ,the heat discharged by HB may be supplied to HEA. the source may ,therefore be eliminated .

the net result is that HEA and HB together consititute a heat engine opearting which is operating in a cycle produce a net work WA WB while exchanging heat with a simple reserviour at T2. This violates the Kelvin Plancks statement of the second law .
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Hence the assumption A > B is wrong Corollary of Carnots theorem

i.

ii.

The efficiency of all reversible heat engines opearating between the same tempearture limit is same. The efficiency of any reversible heat engine operating between two reservoirs is o independent of the nature of the working fluid and o Depends only on the temperature of the reservoirs.

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Efficiency of Reversible heat engine

The efficiency of reversible heat engine in which heat is received solely at T1 is found to be

From the above equation it may be noted that as T2 decreases and T1 increases ,the efficiency of reversible cycle increaes. Since is always less than unity ,T2 is greater than zero and positive. The COP of refrgerator is given by

For a reversible refrigerator,using

Similarly for reversible heat pump ,

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A thermodynamuic temperature scale

A temperature scale that is independent of the properties of the substance that are used to measure the temperature is called a thermodynamice temperatuire scale. The thernodynamic temperature scale can be defined with the help of of reversible heat engine. The thermal efficiency of the reversible heat engine is a function of reserviour temperature only Rev =f (TH,TL) This can be written as as Qh = f (TH,TL) QL

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