PHYSICS MODULE-2

Module-2: 2nd law of Thermodynamics, Entropy & ClausiusClapeyron Relation.

According to first law of thermodynamics, energy is always conserved. The possibility or impossibility of putting energy to use is the subject of the second law of thermodynamics. It also describes the directionality of natural thermodynamic processes. It can be stated in several equivalent forms.

Equivalent Statements Of The Second Law Of Thermodynamics:

The Kelvin statement:
For example, it is easy to convert mechanical work completely into thermal energy, but it is impossible to remove thermal energy from a system and convert it completely into mechanical work with no other changes. This experimental fact is one statement of the second law of thermodynamics. It is impossible to remove thermal energy from a system at a single temperature and convert it to mechanical work without changing the system or surroundings in some other way. Second Law of Thermodynamics: Kelvin Statement

The Clausius statement:

If we place an ice cube on a hot day, the ice cube will melt. From the point of view of energy, what has happened is that some of the heat from the surrounding air enters the ice cube, raising its temperature, and eventually melting it. The surrounding air subsequently cools somewhat. However, nothing from energy conversion, or Newtons law in general, would prevent heat from leaving the ice cube, making the ice cube colder and the surrounding air warmer. Why then doesnt this later phenomena occur? A common example of the conversion of mechanical energy into thermal energy is movement with friction. For example, when a block slides along a rough table, the initial mechanical [kinetic] energy of the block is converted into thermal energy as the block and the table are heated. The reverse process never occurs- a block and table that are warm will never spontaneously cool by converting their thermal energy into kinetic energy that sends the block sliding across the table. Thus there is a lack of symmetry in the roles played by heat and work. This lack of symmetry is related to the fact that some processes are irreversible. It may be mentioned that thermodynamic processes that occur in nature are all irreversible. Let us take the case of heat conduction which is an irreversible process. If we place a hot body in contact with a cold body, heat will flow from the hot body to the cold body until they are at the same temperature. The reverse does not occur; heat does not flow from one to the other making one colder and the other warmer. The answer lies in the Clausius statement of the 2nd law of thermodynamics, which can be written as:

A process whose only final result is to transfer thermal energy from a cooler object to a hotter one is impossible. Second Law of Thermodynamics: Clausius Statement

In other words, Heat never flows spontaneously from low temperature to high temperature. The Refrigerator statement: Refrigerator:
It is impossible to make heat flow from a body at a lower temperature to a body at a higher temperature without doing external work on the working substance. Energy will not flow spontaneously from a low temperature object to a higher temperature object. This precludes a perfect refrigerator.

No cyclic process can transfer heat from a colder place to a hotter place with no input of mechanical work. Second Law of Thermodynamics: Refrigerator Statement

The Heat-engine statement:

The study of the efficiency of heat engines gave rise to the first clear statements of the second law. A heat engine is a cyclic device whose purpose is to convert as much heat input into work as possible. Heat engines contain a working substance [water in a steam engine, air and gasoline vapor in an internal-combustion engine] that absorbs a quantity of heat QH, does work W and gives off heat QC as it returns to its initial state. When we analyze heat engines, it helps us to think of two bodies with which the working substance of the engine can interact. One of these, called the hot reservoir, represents the heat source; it can give the working substance large amounts of heat at a constant temperature TH without appreciably changing its own temperature. The other body, called the cold reservoir, can absorb large amounts of discarded heat from the engine at a constant lower temperature TC. In a steam turbine system, the flames and hot gases in the boiler are the hot reservoir, and the cold water and air used to condense and cool the used steam are the cold reservoir.

We denote the quantities of heat transferred from the hot and cold reservoirs as QH and QC, respectively. When an engine repeats the same cycle over and over, QH and QC represent the quantities of heat absorbed and rejected by the engine during one cycle. The useful output of the engine is the net work W done by the working substance. From the first law,

W = Q = Q H + QC = Q H Q C .
We define thermal efficiency of an engine, denoted by e as the quotient

e=

Q Q W = 1+ C = 1 C QH QH QH

No cyclic process can convert heat completely into work. Second Law of Thermodynamics: Heat-engine Statement This statement of the Second law in terms of the efficiency of a heat engine (Kelvin-Planck statement) can also be written as: The efficiency of a heat engine can never be 100% or more precisely and technically: The maximum efficiency of an engine which operates between two temperatures is given by the Carnot efficiency:

The Entropy statement:

The second law, is rather different from many familiar physical laws. It is not an equation or a quantitative relationship but rather a statement of impossibility. However, the second law can be stated as a quantitative relation with the concept of entropy. Adding heat to a body increases its disorder because it increases average molecular speeds and therefore the randomness of molecular motion. Further expansion of a gas increases its disorder because the molecules have greater randomness of position after the expansion than before. Thus there are two types of disorder in a substance: positional disorder--refers to the distribution of the particles in space. thermal disorder--refers to the distribution of the available energy among the particles.

Entropy and disorder: Entropy provides a quantitative measure of disorder. To introduce this concept, let us consider an arbitrary reversible quasi-static process in which a system consisting of an ideal gas absorbs an amount of heat dQ. According to the first law, dQ is related to the change in the internal energy dU of the gas and the work done dW = PdV by dQ = dU + dW = dU + PdV For an ideal gas, we can write dU in terms of the heat capacity, dU = C V dT , and we can substitute nRT / V for P from the equation of state. Then dQ = C V dT + nRT We can write the Equation as dQ dT dV = CV + nRT T T V The gas is in a more disordered state after the expansion than before because the molecules are moving in a larger volume and have more randomness of position. Thus the fractional volume change dV V

dV is a measure of V dQ . The term T

the increase in disorder, and the above equation shows that it is proportional to the quantity

dT is a measure of thermal disorder which refers to the distribution of the available energy among the T particles. We introduce the symbol S for the entropy of the system, and we define the infinitesimal entropy change dS during an infinitesimal reversible process at absolute temperature T as dS = dQ dT dV = CV + nR T T V

For simplicity, we will assume that CV is constant. Integrating this equation, we get S =

T V dQ = CV ln 2 + nR ln 2 T T1 V1

The above Equation gives the entropy change of an ideal gas that undergoes a reversible expansion from an initial state of volume V1 and temperature T1 to a final state of volume V2 and temperature T2. When an ideal gas undergoes an isothermal expansion, T2 = T1 and its entropy change is S =

V dQ = nR ln 2 T V1

If a total amount of heat Q is added during a reversible isothermal process at absolute temperature T, the total entropy change

S = S 2 S 1 is given by S = S 2 S 1 = Q T

The SI unit of entropy is J/K.

We can generalize the definition of entropy change to include any reversible process leading from one state to another, whether it is isothermal or not. We represent the process as a series of infinitesimal reversible steps. During a typical step, an infinitesimal quantity of heat dQ is added to the system at absolute temperature T. Then we sum [integrate] the quotients

dQ for the entire process; that is, T S =

dQ T 1

The limits 1 and 2 refer to the initial and final states. Because entropy is a measure of the disorder of a system in any specific state, it must depend only on the current state of the system, not on its past history. The change in entropy defined by the above equation does not depend on the path leading from the initial to the final state but it is the same for all possible processes leading from state 1 to state 2. Since entropy is a function only of the state of a system, we can also compute entropy changes in irreversible processes for which above equations are not applicable.

ENTROPY AND THE SECOND LAW: The results of Example about the flow of heat from a higher to a lower temperature, or the mixing of substances at different temperatures, are characteristic of all natural [that is, irreversible] processes. When we include the entropy changes of all the systems taking part in the process, the increases in entropy are always greater than the decreases. In the special case of reversible process, the increases and decreases are equal. Hence we can state the general principle: When all systems taking part in a process are included, the entropy either remains constant or increases. In other words, no process is possible in which the total entropy decreases, when all systems taking part in the process are included. This is an alternative statement of the second law of thermodynamics in terms of entropy. Thus it is equivalent to the engine and refrigerator statements discussed earlier. The increase of entropy in every natural, irreversible process measures the increase of disorder or randomness in the universe associated with that process. Consider again the example of mixing hot and cold water. We might have used the hot and cold water as the high- and low-temperature reservoirs of a heat engine. While removing heat from the hot water and giving heat to the cold water, we could have obtained some mechanical work. But once the hot and cold water have been mixed and have come to a uniform temperature, this opportunity to convert heat to mechanical work is lost irretrievably. The lukewarm water will never unmix itself and separate into hotter and colder portions. No decrease in energy occurs when the hot and cold water are mixed. What has been lost is not an energy, but opportunity, the opportunity to convert part of the heat from the hot water into mechanical work. Hence when entropy increases, energy becomes less available, and the universe becomes more random or run down. The statement of the second law is in terms of entropy: The entropy of a closed system never decreases or equivalently: The change in entropy of the universe is always greater than or equal to zero: Suniv 0.

Change in entropy for different processes:

(1) Entropy changes of a closed system during a reversible process:

A P 1 V B C

Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from state 2 to state 1 along the path B. Since it is a reversible cyclic process

dQ T =0
1B dQ dQ + =0 2B T T 1A 2A

. (i)

Now, consider the reversible cycle from state 1 to 2 along the path A from state 2 to state 1 along path C. For this reversible cyclic process
1C dQ dQ + T 2C T = 0 1A 1B 2A

(ii)

From equations (i) and (ii)

1C dQ dQ = T 2C T 2B

This shows that

dQ T

has the same value for all the reversible paths from state 2 to state 1. This quantity is

independent of path and is a function of the end states only, therefore it is a property. This property is called entropy and defined by the relation

dS =

dQ T

The change in entropy is then the inverse of the temperature integrated over the change in heat transfer.

dS =
1 1

d Q T

S 2 S1 =

dQ T 1

The quantity S2 S1 represents the change in entropy of the system when it is changed from state 1 to state 2.

(2) Entropy changes of a closed system during an Irreversible process:

Consider a closed system undergoing a reversible process from state 1 to state 2 along the path A and from state 2 to state 1 along the path B. For a reversible cyclic process

dQ
2A

=0.
1B

2
.. (i)

dQ dQ + T 2B T = 0 1A

A P 1 V B C
irreversible

Now consider an irreversible path C from state 2 to state 1.

dQ 0 Applying Clausius inequality for the cycle of process A and C T

So,

dQ dQ + 0 T T 1A 2C

2A

1C

(ii)

From equations (i) and (ii)

1B

dQ dQ T 2 T 0 2B C
1B 1C

1C

Since path B is reversible and entropy is a property

1B

dQ B T = 2BdS = 2CdS 2 dQ T

dS

or S2 S1

dQ T

The above equation shows that the effect of irreversibility is always to increase the entropy of a system.

(3) Adiabatic Process: We know that the heat absorbs in a reversible adiabatic process is zero. Hence, for
such a process entropy change is given by

dS =

dQ =0 T

S = Constant That is Entropy of a system remain constant for a reversible adiabatic process.

(4) Isothermal process: If Q amount of heat absorbed during an isothermal process at constant
temperature T, the change of entropy,

dS =

dQ Q = T T

Change in Entropy (Carnots Cycle):

(1) Reversible process: In a Carnot cycle, the change in entropy of the working substance is zero.
This reversible system consists of a source at T1, the working substance and the sink at T2. The loss of entropy (here heat is denoted by Q) of the source is T and the gain of entropy of the sink is T . 1 2 The net gain of entropy of the system is dS = (
Q1
Q2

Q1 Q 2 ). T1 T2 Q1 Q 2 = T1 T2 Q1 Q 2 =0 T1 T2

We know, for Carnot cycle

That is entropy of the whole system remains constant.

(2) Irreversible process: The efficiency of an irreversible engine absorbing heat Q1 at T1 and rejecting
heat Q2 at temperature T2 is given by

Q1 Q 2 Q1

Again, the efficiency of a reversible engine is given by temperatures. According to Carnot theorem,

T1 T2 , working between the same two T1

< T1 T2 Q1 Q 2 Or, < Q1 T1

Or, 1-

Q2 T2 <1Q1 T1

Or, Or, Or,

Q2 T2 > Q1 T1 Q 2 Q1 > T2 T1 Q 2 Q1 >0 T2 T1

Q2 Q1 is the gain in entropy of the sink and is the loss of entropy of the source. The change of entropy of the T2 T1
working substance is zero as it returns to the original state at the end of a complete cycle.

The net gain in entropy of the system =

Q 2 Q1 = positive. T2 T1

So the entropy increases in a irreversible process.

Clausius-Clapeyron Relation:
The Clausius-Clapeyron relation, in thermodynamics, is a way of characterising the phase transition between two states of matter, such as solid and liquid. On a pressure-temperature (P-T) diagram, the line separating the two phases is known as the coexistence curve. The Clausius-Clapeyron relation gives the slope of this curve Mathematically,

dP L = dT TV
where

dP is the slope of the coexistence curve, L is the latent dT

H E A P D T T+dT dP C G F

heat, T is the temperature, and V is the volume. Consider the isothermals FBAE at temperature T + dT and GCDH at temperature T. Here EA and HD show the liquid state of the substance. At A and D the substance is purely in the liquid state (as shown in Fig.). From A to B or D to C the substance is in transition from the liquid to the gaseous state and vice versa. At B and C the substance is purely in the gaseous state. From B to F or C to G the substance is in the gaseous state. Join A to D and B to C by dotted lines.

V1 V

V2

The cycle ABCD represents a complete cycle and Carnots theorem can be applied. Suppose the volume at the point A is V 1 and temperature T+dT. The presssure is just below its saturation pressure and the liquid begins to evaporate and at the point B the volume is V2. The substance is in the vapour state. Suppose the mass of the liquid at B is one gram. The amount of heat absorbed is Q1. Here Q1 = L + dL Where, L + dL is the latent heat of the liquid at temperature (T + dT). At the point B, the pressure is decreased by dP. The vapour will expand and its temperature T, the gas begins to condense and is converted into the liquid state. At the point D, the substance is in the liquid state. From C to D, the amount of heat rejected is Q2. Here Q2 = L, where L is the latent heat at temperature T. By increasing the pressure a little, the original point A is restored. The cycle ABCDA is completely reversible. Applying the principle of the Carnots reversible cycle

Q1 Q 2 = T1 T2 Q1 Q2 T1 T2 = Q2 T2
The area of the figure ABCD = Q1 Q2 = dL = dP (V2 V1)

or

Q1 T1 = Q 2 T2

dL dT = L T
Here, Q1 = L + dL, T1 = T + dT, Q2 = L, T2 = T

dP (V 2 V1 ) dT T1 T2 = T + dT T = dT = L T dP L = (1) dT T (V 2 V1 )
This is called the Clapeyrons latent heat equation.

Q1 Q2 = L + dL - L = dL

Applications:
(1) Effect of change of pressure on the melting point.
dP is a positive quantity. dT

When a solid is converted into a liquid, there is change in volume. (i) If V2 is greater than V1, then

It means that the rate of change of pressure with respect to temperature is positive. In such cases, the melting point of the substance will increase with increase in pressure and vice versa. (ii) If V2 is less than V1, then

dP is a negative quantity. dT

It means that the rate of change of pressure with respect to temperature is negative. In such cases, the melting point of the substance will decrease with increase in pressure and vice versa. In the case of melting ice, the volume of water formed is less than the volume of ice taken. Hence, V2 < V1. Therefore, the melting point of the ice decreases with increase in pressure. Hence ice will melt at a temperature lower than zero degree centigrade at a pressure higher than the normal pressure. Ice melts at 0 o C only at a pressure of 76 cm of Hg.

(2)

Effect of change of pressure on the boiling point.

When a liquid is converted into a gaseous state, the volume V2 of the gas is always greater than the corresponding volume V1 of the liquid i.e. V2 > V1. Therefore,

dP is a positive quantity. dT

With increase in pressure, the boiling point of a substance increases and vice versa. The liquid will boil at a lower temperature under reduced pressure. In the case of water, the boiling point increases with increase in pressure and vice versa. Water boils at 100 oC only at 76 cm of Hg pressure. In the laboratories, while preparing steam, the boiling point is less than 100 oC because the atmospheric pressure is less than 76 cm of Hg. In pressure cookers, the liquid boils at a higher temperature because the pressure inside is more than the atmospheric pressure.

10

SOLVED PROBLEMS
Problem No. 1: One kilogram of ice at 00C is melted and converted to water at 00C. Compute the change in entropy, assuming that the melting is done reversibly. The heat of fusion of water is Lf = 3.34x105 J/kg. Solution: The heat needed to melt the ice is Q = mLf = 3.34x105 J

Q 3.34 x10 5 J S = S 2 S 1 = = = 1.22 x10 3 J / K . T 273 K

This increase corresponds to the increase in disorder when the water molecules go from the highly ordered state of a crystalline solid to the much more disordered state of a liquid. When we refreeze the water, Q has the opposite sign, and the entropy change of water is

S = 1.22 x10 3 J / K .
The water molecules rearrange themselves into a crystal to form ice, so disorder and entropy both decrease. Problem No. 2: One kilogram of water at 00C is heated to 1000C. Compute its change in entropy. Solution: We know dQ = mcdT. So,

S = S 2 S 1 =
1

2 T dQ dT 373 K = mc = mc ln 2 = [1.00kg ][4190 J / kg.K ][ln ] = 1.31x10 3 J / K T T1 273 K 1 T

Problem No. 3: Suppose 1.00 kg of water at 100 0C is placed in thermal contact with 1.00 kg of water at 0 0C. What is the change in entropy? Assume that specific heat capacity of water is constant at 4190 J/kg.K over this temperature range. Solution: The final temperature = 50 0C = 323 K. The entropy change of the hot water = mc
T2 T1 323 K dT 323 K dT = [1.00kg ][ 4190 J / kg.K ] = [ 4190 J][ln ] = 603 T T 373 K 373 K

J/K

The entropy change of the cold water =[4190 J/K][ln(323/273)] = 705 J/K. Therefore, the total entropy change of the system = -603+705 = 102 J/K Problem No. 4: Find the entropy change for the isothermal expansion of 0.75 mol of an ideal gas from V 1 = 1.5 L to V2 = 3 L. Solution: The change in entropy can be calculated from S = V Q = nR ln 2 = [0.75mol][8.31 J / mol.K ][ln 2 ] = 4.32 T V1 J/K

11

Problem No. 5: An inventor claims to have constructed an engine that has an efficiency of 75% when operated between the boiling and freezing points of water. Is it possible? Solution: The efficiency of a real engine [with its irreversible processes and wasteful energy transfers] must be less than the efficiency of a Carnot engine operating between the same two temperatures. The efficiency of a Carnot engine operating between the boiling and freezing points of water is

= 1

TL 273 = 1 = 0.268 27 % TH 373

Thus the claimed efficiency of 75% for a real engine operating between the given temperatures is impossible.

12

Problem Sheet - Entropy

1. Imagine a Carnot engine that operates between the temperatures TH = 850 K and TL = 300 K. The engine
performs 1200 J of work each cycle, which takes 0.25 s. [a] What is the efficiency of this engine? [b] What is the average power of this engine? [c] How much energy is extracted as heat from the high-temperature reservoir every cycle? [d] How much energy is delivered as heat to the low-temperature reservoir every cycle? [e] What is the entropy change of the working substance for the energy transfer to it from the hightemperature reservoir? From it to the low-temperature reservoir?

2. A carnots engine has an efficiency of 22.0%. It operates between constant-temperature reservoir in

temperature by 750 C. What are the temperatures of the two reservoirs?

3. Calculate the change in the melting point of naphthalene for one atmosphere rise in pressure given that its
melting point is 80 oC. Latent heat of fusion is 4563 cal/mol and increase in volume on fusion is 18.7 cm3 per mol and 1 calorie = 4.2107 ergs.

4. Calculate

the pressure required to lower the melting point of ice by 1oC. 0 3 0 (L = 79.6 cal/g, specific volume of water at 0 C = 1.000 cm , specific volume of ice at 0 C = 1.091 cm3 and 1 atmosphere pressure = 1.013106 dynes/cm2). temperature. What is the change in entropy for a complete cycle?

5. A Carnot engine operates between 240 0C and 100 0C, absorbing 3.35 x 105 J per cycle at the higher 6. Calculate the change in entropy when 150 gm of ice at 0 OC is converted into steam at 100 OC. Specific
heat of ice = 0.5 cal/gm K, latent heat of ice = 80 cal/g, latent heat of steam = 540 cal/g.

7. Water boils at a temperature of 101 0C at a pressure of 787 mm of Hg. 1gram of water occupies 1,601 cm3
on evaporation. Calculate the latent heat of steam. (J = 4.2 106 ergs/cal)

8. Five moles of an ideal gas undergo a reversible isothermal expansion from volume V1 to volume V2 = 4 V1
at temperature T = 450 K. Find [i] work done by the gas and [ii] the entropy change of the gas. [iii] If the expansion is reversible and adiabatic instead of isothermal, what is the entropy change of the gas?

9. A 10 g ice cube at -100C is placed in a lake whose system temperature is 150C.Calculate the change in
entropy of the ice cube-lake system as the ice cub e comes to thermal equilibrium with the lake. The specific heat of the ice is 2220 J/kg.K.

10. The melting point of a lead is 327 0 C and the latent heat of its fusion is 5.86 cal. per gm. Calculate the
changes of entropy when 4 gm-molecules of lead are used ( Atomic weight of lead = 207)

11. 1 kg of water at 1000 C is mixed with 1 kg of water at 00 C, the common temperature being 500 C, what is
the change of entropy? Consider the entropy of water to be zero when its it is in the liquid phases at 0 0 C and atmospheric pressure.

13