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SECOND LAW OF THERMODYNAMICS

The 1st Law of Thermodynamics gives us the idea on the conservation of energy, that is in any given process, energy cannot

be created nor destroyed but can only change in form. However


the existence of energy balance does not suffice to answer all questions about a given process. Consider the following example: A. A cup of hot coffee left in a cool room eventually cools off B. A cup of hot coffee getting hotter in a cooler room While both process would nor violate the first law, we can tell from experience that only process A will actually occur. Thus it can be said that processes proceed in a certain direction only. The inadequacy of the First Law to identify whether a process can take place is remedied by introducing another general principle, the Second law of Thermodynamics. In general the second law is: useful in identifying whether a certain process can take place

also asserts that energy has quality as well as quantity also used in determining theoretical limits for performance of

commonly used engineering systems such as heat engines, and refrigerators as well as predicting the degree of completion of chemical reactions. Quality Work can be readily transformed into other forms of energy for example to potential energy by lifting weight, to kinetic energy by acceleration of mass etc.. and these conversions can be made to approach 100%. However the reverse process ,for example conversion of heat to work, is not possible. Consider the Figure below
WORK NO WORK

HEAT
WATER WATER

HEAT

Figure 1. Conversion of Work to Heat

Figure 2. Conversion of Heat to Work

Conversion of work to heat is shown in Figure 1. The mechanical work done by the shaft first increase the internal energy of the water which may then leave the water as heat. However the reverse of this process as shown in figure 2 is not possible because transferring heat to water will not cause the shaft to rotate. This leads us to conclude that work is a higher form of energy than heat because while conversion of heat to work can be done directly at a maximum of 100% conversion, the reverse, conversion of heat to work (by the use of special devices called heat engines), do not exceeds about 40% efficiencies. This difference in quality of energy is the

basis of the Second Law of Thermodynamics

Two Classical Statement of the Second Law

1. Kelvin Planck Statement - It is impossible to construct an engine that,


operating in a cycle will produce no effect, other than the extraction of heat from the reservoir and the performance of an equivalent amount of work.

2. Clausius Statement - It is impossible to construct a device that,


operating in a cycle, will produce no effect other than the transfer of heat from a cooler to hotter body

The first statement as discussed earlier is a consequence of the difference in the quality of energy and is basically derived from the experienced limitations of Heat engines ( example., efficiency of most steam power plants do not exceed about 40 %). The second statement on the other hand is also a valid statement of the second law and is related to the operation of heat pumps and refrigerators.

EQUIVALENCE OF THE TWO STATEMENTS

Although the two statements seemed to be of different context, they are actually equivalent in their consequence. Consider for example the following figure.
High T Reservoir
QH Wnet = QH
Refrigerator

High T Reservoir
QH + QL QL

Engine 100%

Refrigerator

QL

QL

Low T Reservoir FigureA. !00% Efficent Engine


driving a Refrigerator

Low T Reservoir FigureB. Net Result of Process in Fig2,


Transfer of Heat from TL to TH

QH is completely converted into work, which in turn, is used to drive a refrigerator that extracts QL from the Low temperature reservoir, The refrigerator, by force balance, will reject heat of amount (QH = W) + QL to high temperature reservoir. But since QH has been previously supplied by the High Temp reservoir to heat engine, then the High Temp reservoir receives a net amount of QL. Consequently, this is equivalent to figure B where QL is being transferred from a cooler body to a hotter body without any expenditure of work; a clear violation of the second statement. Thus the violation of statement 1 resulted to the violation of statement 2.

The Kelvin Planck statement is violated in the Process shown in figure A, where heat absorbed

Heat Engines As previously discussed, heat cannot be directly and completely converted to work ,as a consequence of the difference in the quality of Energy,. But we can convert part of heat to work by the use of the devices called heat engines. Heat engines are devices that operate in thermodynamic cycle and do a certain amount of net positive as a result of heat transfer from a high temperature body to a low temperature body. Generally Heat Engines are characterized by the following: 1. 2. 3. 4. They receive heat from a high temperature source (solar energy, oil furnace, nuclear reactors etc.) They convert part of this heat to work ( usually in the form of a rotating shaft). They reject the remaining waste heat to a low temperature sink (atmosphere, rivers, lakes, etc.) They operate in a cycle.

ENERGY SOURCE

QH
BOILER

Win
PUMP TURBINE

Wout

CONDENSER

QL
ENERGY SINK

Working Fluid

the fluid involved in the cyclic process, to and from which heat is transferred is called the

Examples of Heat Engines: Steam power Plants, Carnot Engine, Internal Combustion Engines ex. Car engines and gas turbine. (In internal combustion engines, the working fluid does not undergo complete cycle)

Thermal Energy Reservoir


that can supply or absorb finite amounts of heat without undergoing any change in temperature Examples: Rivers, lakes, oceans, atmospheric air, industrial furnace etc.
- a hypothetical body with a relatively large thermal energy capacity ( mass x specific heat),

Thermal Efficiency
- the fraction of heat input that is converted to net work output

= net work output


heat input since Wnet = Qin - Qout

Wnet Qin

= Wnet Qin

= =1-

Qin - Qout Qin Qout Qin

(absolute signs are used to make the equations independent of the sign convention of Q and W)

Notice that for the efficiency to be 100 % Q out must be zero. But no engine has ever been built for which this is true, some heat is always (and must be) rejected to the cold reservoir to complete the cycle. This actual experience just confirms statement 1 of the second law.

Reversible and Irreversible Processes

Reversible Processes are hypothetical process that can be

reversed without leaving any trace to the surrounding by contrast heat flow with finite temperature difference, free expansion of gas and conversion of work to heat are irreversible because they cannot be reversed without leaving any change to the surroundings. From these examples we can deduce that reversible processes are possible only if the net heat and net work exchange between the system and surroundings is zero (original and reverse) and this is true if the process is isothermal and adiabatic Reversible process actually do not occur in nature, they are merely idealization but they can be approximated by actual devices by making the temperature gradients and pressure differences as small as possible. Engineers are interested in reversible processes because they are the most efficient processes where work producing device such as steam turbines deliver the most work and work consuming devices such as compressors consume least work

The Carnot Engine


Second law no heat engine can have a thermal efficiency of 100%. What then is the upper limit of the efficiency of the heat engine operating between two heat reservoirs TH and TC ??.. This question was answered by Sadi Carnot in 1824. Carnot is a French Engineer who developed the Carnot Cycle,an idealized heat engine that has the possible maximum efficiency Overall efficiency of the cycle depends on the individual processes making up the cycle; o thus by using / utilizing processes that require the least amount of work and deliver the most we can actually achieve a maximum efficiency. o Such is the case when reversible processes are used. o Consequently to make the process ideal, every process in the cycle must either be adiabatic or isothermal (reversible processes).

Carnot Engine:
A heat engine operating in a completely reversible manner Operates between two heat reservoirs in such a way that all heat absorbed is absorbed at the constant temperature of the hot reservoir and all heat rejected is rejected at the constant temperature of the cold reservoir It consists of four steps: 2 reversible adiabatic and 2 reversible isothermal processes It may be operated in reverse and becomes a reversible refrigeration cycle It is considered as the most efficient cycle

Four Basic Processes of Carnot Cycle: 1. A reversible ISOTHERMAL PROCESS in which heat is transferred to or from the high temperature reservoir 2. A reversible ADIABATIC PROCESS in which the temperature of the working fluid decreases from the high temperature to the low temperature reservoir. 3. A reversible ISOTHERMAL PROCESS in which heat is absorbed to or from the low temperature reservoir 4. A reversible ADIABATIC process in which the temperature of the working fluid increases from the low temperature to the high temperature reservoir. Note : If every process involves in a cycle is reversible, the cycle is also reversible.

Two Propositions regarding the Carnot Cycle 1. It is impossible to construct an engine that operates between two given reservoirs and is more efficient than a reversible engine operating between the same two reservoirs. 2. All engines that operate on a Carnot Cycle between the two given constant temperature reservoirs have the same efficiency regardless of the working fluid.

High T
QH

High T
QH

Wout
QL

Wout
QL

LowT Reservoir

LowT Reservoir

If Engine E has the same process as C, the efficiency is the same regardless of the working fluid

The Thermodynamic Temperature Scale


As mentioned, the efficiency of Carnot Cycle is independent of the working substance and depends on Temperature only =1QL = f ( TL, TH) QH

derive the functional relation of QL/QH = f( TL, TH)

Consider the following figure


T1 Q1 WA
A

Q1

Q2
T2 Q2 WB
B

WC

Q3

Q3 T3

For all three heat engines we have, Q1 / Q2 = f(T1, T2) Q2/Q3 = f(T2/T3) Q1/Q3 = f(T1, T3)

Consider the equation Q1 = Q1 X Q2 Q3 Q2 Q3 Which Corresponds to: f(T1, T3) = f(T1, T2), f(T1, T3)

This condition is satisfied if the function f has the following form f(T1, T2) = (T1) (T2) and f(T1, T3) = (T2) (T3)

So that(T2) will cancel Q1 = f(T1, T3) =(T1) Q3 (T3) Thus for a reversible heat engine operating between the two reservoirs of temperatures TL and TH QH QL =(TL) (TH)

Several functions =(T) will satisfy this equation and the choice is arbitrary. Lord Kelvin first proposed taking (T) = T to define a thermodynamic temperature scale. QH QL = TH TL

Kelvin scale and temperature on this scale are called absolute temperatures. Thus the Thermal Efficiency can be redefined as: =1TL TH

Problems: 1. A central power plant rated at 800,000kW generates steam at 585 K discards heat to a river at 295K. If the thermal efficiency of the plant is 70% of the maximum possible value, how much heat is discarded to the river 2. A fuel furnishes 7000 cal of heat per gram. Calculate the maximum work obtained from this heat in an engine, which operates with water between its boiling point and 40C. determine the thermal efficiency. 3. An inventor claims to have developed an engine that takes in 25,000J/s at a temperature of 400K, rejects 12,000J / sec at a temperature of 200K and delivers 15kW of mechanical power. Would you advise investing money to put this engine on the market.

Entropy This is an intrinsic property of a system, functionally related to the measurable coordinates, which characterize the system. For a reversible process,
dS

This is a property of matter that measures the degree of randomization or disorder at the macroscopic level. It owes its existence to the Second Law of Thermodynamics, from which it arises in much the same way as internal energy does from the First Law of Thermodynamics. The change in entropy of a system caused by heat transfer can always be calculated by dS Q , whether the heat transfer is accomplished reversibly or irreversibly. Entropy is a state function or property During a reversible adiabatic process, the entropy of a system is constant and the process is said to be isentropic Statement of the Second Law of Thermodynamics The entropy change of any system and surroundings, considered together, is positive and approaches zero for any process which approaches reversibility. In mathematical form ( S )total 0 ( S )surroundings 0
T

Q T

( S )system +

Where > refers to the irreversibility of the process = refers to the reversibility of the process

Thus for an irreversible process ( S )total > 0

For a reversible process ( S )total and


Ssystem

=
T

0
Ss u r r Qs u r r T

Q system

Dependency of Entropy on the Variables of A system 1. S = f(T,V)


S T S V
T2 T1

dS

dT
V

dV
T

Cv dT T

V2 V1

P T

dV
V

For an Ideal Gas


S nC v ln T2 T1 nR ln V2 V1

If T is Constant
S nR ln V2 V1
T2 T1

If V is Constant,
S nCV ln

2. S = f(T,P)
dS S T dT
P

S P

dP
T

T2 T1

CP dT T

P2 P1

V T

dP
V

For an Ideal Gas


S nC P ln T2 T1 nR ln P2 P1

If T is Constant
S nR ln P1 P2 T2 T1

If V is Constant,
S nC p ln

Problems:
1. Heat is transferred directly from a heat reservoir at 540F to another heat reservoir at 40F. If the
amount of heat transferred is 100 Btu, what is the total entropy change as a result of the process?

2. If 2 kg of liquid water at 90 is mixed adiabatically at constant pressure with 3 kg of liquid water at 10,

what is the total entropy change resulting from this process?. For simplicity take the heat capacity of water to be constant at Cp = 1 cal/g or 4184J/kg K.

3. A lump of copper having a mass of 10 lbs at a temperature of 1000F is dropped into a well insulated
bucket containing 100 lbs of water at a temperature of 70F. If the specific heats of copper and water are 0.095 and 1.00 respectively, calculate the resulting changes in entropy of the water and copper, and calculate the total entropy change resulting from the process.

4. A heat exchanger is to be constructed in which air ( assume Cp=7 ) is to be heated from 70 to 200F bay
another stream of air, originally at 350F. Equal amounts of heated air and heating air are to be used. Assume that heat losses from the exchanger are negligible. a. calculate the entropy changers of the heated air and the heating air for both parallel and countercurrent flow in the exchanger. b. What is the total entropy change in each gas.