Entropy (S) is a term coined by Rudolph Clausius in the 19th century. Clausius was convinced of the significance of the ratio of heat delivered and the temperature at which it is delivered. Entropy can be thought of as a measure of the randomness of a system.
Entropy (S) is a term coined by Rudolph Clausius in the 19th century. Clausius was convinced of the significance of the ratio of heat delivered and the temperature at which it is delivered. Entropy can be thought of as a measure of the randomness of a system.
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Entropy (S) is a term coined by Rudolph Clausius in the 19th century. Clausius was convinced of the significance of the ratio of heat delivered and the temperature at which it is delivered. Entropy can be thought of as a measure of the randomness of a system.
Copyright:
Attribution Non-Commercial (BY-NC)
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Download as PPTX, PDF, TXT or read online from Scribd
The First Law of Thermodynamics states that energy cannot be created nor destroyed. Therefore, the total energy of the universe is a constant. Energy can, however, be converted from one form to another or transferred from a system to the surroundings or vice versa. Spontaneous Processes Spontaneous processes are those that can proceed without any outside intervention. The gas in vessel B will spontaneously effuse into vessel A, but once the gas is in both vessels, it will not spontaneously Spontaneous Processes Processes that are spontaneous in one direction are non spontaneous in the reverse direction.
Reversible Processes In a reversible process the system changes in such a way that the system and surroundings can be put back in their original states by exactly reversing the process.
Changes are infinitesimally small in a reversible process Irreversible Processes Irreversible processes cannot be undone by exactly reversing the change to the system. All Spontaneous processes are irreversible. All Real processes are irreversible. Entropy Entropy (S) is a term coined by Rudolph Clausius in the 19th century. Clausius was convinced of the significance of the ratio of heat delivered and the temperature at which it is delivered, Entropy can be thought of as a measure of the randomness of a system. It is related to the various modes of motion in molecules.
For a process occurring at constant temperature (an isothermal process)
Like total energy, E, and enthalpy, H, entropy is a state function. Therefore, AS = S final S initial
q rev = the heat that is transferred when the process is carried out reversibly at a constant temperature. T = temperature in Kelvin. Entropy and Nature of Process The definition requires following specifications : 1. The amount of heat transferred 2. The temperature level at which the transfer occurs 3. The nature of process whether it is reversible or irreversible To comply with these requirements we define entropy change as : dS= dQR/T Where , S=Entropy Q=Heat transferred T=Absolute Temperature R=Reversibilty of Process
Entropy and Heat When a certain form of energy is transferred into heat, the total energy gets degraded with an increase in the entropy of the system E.g.: Consider 1 kg of water at the top of mountain at a height of 426.8 m. At this position water has a potential energy of 4.187 kJ (P.E=m*g*h=1*9.81*426.8=4.187kJ) When water falls and strikes the river at bottom all its PE gets converted into thermal energy with a temperature rise of water by approx 1 K
This results in the degradation of the total energy. If not then reverse the process and raise the water to its initial position by cooling it by 1 K The degradation of energy is measured by the net increase in entropy Here increase in entropy was due to the degradation of the mechanical energy into heat In short the increase in the entropy is due to the addition of heat through any form of source or any mechanism The increase in entropy is proportional to the heat exchanged but not equal to it Therefore it is necessary to consider the temperature of the system when heat is transferred Second Law of Thermodynamics The entropy of the universe increases (real, spontaneous processes). But, entropy can decrease for individual systems. Entropy Changes Entropy changes for a reaction can be calculated the same way we used for AH:
S for each component is found in a table. Note for pure elements:
Practical uses: surroundings & system Entropy Changes in Surroundings Heat that flows into or out of the system also changes the entropy of the surroundings. For an isothermal process:
Practical uses: surroundings & system At constant pressure, q sys is simply AH for the system.
Practical uses: surroundings & system
Entropy Change in the Universe The universe is composed of the system and the surroundings.
Therefore, AS universe = AS system + AS surroundings
For spontaneous processes AS universe > 0
Practical uses: surroundings & system = Gibbs Free Energy Entropy-2 2 1 1 2 2 2 2 2 1 1 1 1 2 1 2 1 1 2 0 From entropy definition Q Q dS= , 0 Therefore, rev rev rev rev rev rev Q Q Q T T T Q Q dS T T T T Q Q dS S S S T T Q S S S T o o o o o o o o o o | | | | = + s | | \ . \ . | | | | | | | | = = = + | | | | \ . \ . \ . \ . | | | | s = = = A | | \ . \ . | | A = > | \ . } } } } } } } } } } 2 1 , This is valid for all processes Q Q , since = , T T rev irrev Q dS dS dS T o o o | | | | > > | | \ . \ . } 1 2 reversible process any process T S Entropy-2 The entropy change during an irreversible process is greater than the integral of oQ/T during the process. If the process is reversible, then the entropy change is equal to the integral of oQ/T. For the same entropy change, the heat transfer for a reversible process is less than that of an irreversible. Why?
Entropy Increase Principle 2 2 1 gen 1 2 2 2 1 1 1 , define entropy generation S where 0. If the system is isolated and "no" heat transfer The entropy will still increase or stay system gen gen Q S S S T Q Q S S S S T T S o o o | | A = > | \ . | | | | A = = + > | | \ . \ . > } } } the same but never decrease 0, entropy increase principle system gen S S A = > Entropy Increase Principle A process can take place only in the direction that complies with the increase of entropy principle, that is, S gen >0.
Entropy is non-conservative since it is always increasing. The entropy of the universe is continuously increasing, in other words, it is more disorganized and is approaching chaotic.
The entropy generation is due to the existence of irreversibilities. Therefore, the higher the entropy generation the higher the irreversibilities and, accordingly, the lower the efficiency of a device since a reversible system is the most efficient system.
Mathematical statement of Second Law The diagram besides shows a system undergoing a reversible (1a2b1)and an irreversible(1a2c1) cycle Suppose that the system is taken from the initial state 1 to final state 2 along a reversible path a and then restored to the initial state through irreversible path b 1 2 b a T S c Application of Clausius inequality to the reversible cycle 1a2b1 is : suppose given cycle is irreversible. If this is replaced by a large no. of infinitesimal cycles some of them are reversible and some are irreversible. The Carnot principle states that a reversible heat engines more efficient than an irreversible engine. The efficiency of a reversible engine is
Now consider an irreversible engine operating between the same thermal reservoir. Let dQ1 = Heat absorbed by the engine. dQ2 = Heat rejected by the engine. The efficiency of engine is
Then by Carnot principle,
< < <
< 0 Applying sign convention , Heat rejected dQ2 is negative. Above equation becomes + + < 0 An irreversible cyclic operation can be divided into a no of heat engine cycles involving heat interactions. For each such cycle it is possible to write equation analogous to the above equation, so that the net result is Where , T: temperature of thermal reservoir Combining equation for reversible and irreversible cycle we get Above equation is known as Clausius inequality. It states that in a cyclic operation the sum of terms around a complete cycle is less than or equal to zero depending on whether the process is reversible or irreversible.