INTRODUCTION TO THE SECOND LAW Clausius Statement It is impossible for any system to operate in such a way that the

e sole result would be an energy transfer of heat from a cooler to a hotter body. Kelvin-Planck Statement It is impossible for any system to operate in a thermodynamic cycle and deliver a net amount of energy by work to its surroundings while receiving energy by heat transfer from a single thermal reservoir. Application to Power Cycles: I. Carnots Theorem The thermal efficiency of any irreversible power cycle is always less than that of a reversible power cycle when each operate between the same two thermal reservoirs. II. Carnots Corollary All reversible power cycles operating between the same two thermal reservoirs have the same thermal efficiency.
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IIIa. Maximum Work Corollary: No change in state of a system communicating with a single reservoir can produce more work in the surroundings than the same change carried out reversibly. This is the maximum amount of work that can be produced by the change in state. Proof: Consider an irreversible cycle, I, with two reversible cycles, RA and RB, returning the system to its initial state.

RB

RA

IIIa. Maximum Work Corollary: Consider a cycle composed of processes I and RA, such that WI > 0 and WR < 0. This A cycle produces net work on the system. This is allowed by the Kelvin-Planck statement of the second law. Since RA is reversible, it can be run in the reverse direction such that WR > 0, and A then both WI > 0, WR > 0 and WR > WI. This is allowed by the second law.
A A

RA

WR > WI A Allowed by second law.!

IIIa. Maximum Work Corollary: Now, consider a cycle composed of processes I and RB, such that WI > 0 and WR < B 0. This cycle produces net work in the surroundings. This is not allowed by the Kelvin-Planck statement of the second law. Reversing RB now has the effect that WR > 0, and then both WI > 0, WR > 0 and B A WR < WI. This is not allowed by the second law.
B

RB

WR < WI B Not allowed by second law.!

IIIa. Maximum Work Corollary: Conclusion: No change in state of a system communicating with a single reservoir can produce more work in the surroundings than the same change carried out reversibly.

RA

WR > WI A Allowed by second law.!

IIIb. Minimum Work Corollary: The minimum amount of work required to change the state of a system is that which is done reversibly. Proof: Consider an irreversible cycle, I, with two reversible cycles, RA and RB, returning the system to its initial state; etc. WR > W I A Net work on surroundings > 0 Not allowed by second law. WR < WI B Net work on system > 0 Allowed by second law.! WR < WI B Reversible work is minimum required to change state. V
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RB

RA

Universal Temperature Scales

! If we only knew about the second law, we could still set up a universal temperature scale, independent of the properties of particular substances, that depended only on reversibility. ! Pick some standard reversible efficiency d!R, such as d!R, = 0.01 (1%). This standard efficiency can define a temperature difference or temperature ratio: ! + d! !" d!R ! ! Difference scale: d!/! = d!R (e.g., 1% change in efficiency defines 1 degree) ! Ratio Scale: (! + d!)/! = 1 + d!R ! Kelvins first scale: d!/! = d ln! = d!R (e.g., 1% efficiency is 1% change in temperature) [But this was not done for historical reasons.]
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Universal Temperature Scales

! Joule pointed out to Kelvin that if the temperatures were defined in terms of the two heats, QH and QC, the thermodynamic scale would coincide with the ideal gas temperature scale. (This also requires the first law.)

! It can be shown that the dependence on " can be separated as:

! Can then choose

Kelvins second scale.

Universal Temperature Scales

Proof: QR1
R1

WR1 QR2 QR2

R2

WR2 QR3

That is, the dependence on "2 must cancel out! This is only possible if:

To complete the definition: Q is the thermometric property independent of nature of working substance.
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Universal Temperature Scale

Comments: (1)! The temperatures are either all positive or all negative no mixing of signs. (2)! This scale exhibits T = 0, which is an aribitrary value. - For example, Kelvins first scale (lnT # $) ranges from -# to +# (3) (4) How do we know this is the same as the ideal gas temperature scale?

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Relationship Between Ideal Gas Temperature and Kelvin Temperature

Carnot cycle for ideal gas is composed of two adiabatics and two

isotherms:

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Relationship Between Ideal Gas Temperature and Kelvin Temperature

First law for an ideal gas:

Along the two isotherms:

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Relationship Between Ideal Gas Temperature and Kelvin Temperature

Along the two adiabatics ($Q = 0):

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Clausius Theorem (Clausius Inequality) Defines the state function entropy, and the direction that processes must take towards equilibrium. Motivation: Notice that irreversible cycles differ from reversible ones they have lower efficiencies. - Can this difference be converted into something more general that
distinguishes irreversible processes from reversible ones? This would be the key to the direction into which all real processes must go.

Plan of attack:
-! Take some system around a series of processes so that it ends up in the same state (any system, any series of processes). -! In doing so it exchanges heat with a number of sources or sinks. -! Now restore everything to their initial states and account for what is left over. - It will turn out to always have the same sign (or zero). This is essentially the one-wayness of the real world.
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SUPER SYSTEM

SYSTEM

WSYS

Q1 T1 Q1 W1 W2 Q10

Q2 T2 Q2 11111111! Wi Q20

Qi Ti Qi 11111111! W1 Qi0

Qn Tn Qn Qn0

"#$!%&'()*&(+,-(!.&+,!%&/&(0-)(!
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For Super System: Drop all absolute signs on Qs and Ws, and treat the quantities as algebraic. Make a Qi = -Qi . This restores all the reservoirs. After everything has occurred, the SYSTEM plus all the reservoirs are back to their initial states and have exchanged heat with only one reservoir at T0, and the SUPER SYSTEM has undergone a cycle. Perform analysis with first and second laws.

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For Super System:

First law: Second law: (Kelvin-Planck)

(Super System cannot produce work in surroundings) Combine first and second laws: And since: Since T0 > 0: (1)! $Q refers to the System with respect to sign convention; (2)! T refers to the reservoir that supplies $Q, not the temperature of the system (which is unknown and may vary in different parts)

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Summary:
Whenever any system undergoes a cyclic transformation (process), the integral of $Q/T around the cycle is < 0 (Clausius Inequality)

Clausius #1: For a reversible cycle (actually for any cycle) Run it in reverse: Thus, for a reversible process: So: must be independent of process, as long as it is reversible.

Proof: Proceed reversibly by Process A, then back reversibly by Process B:

Independent of Process A or B.

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Entropy

Clausius #2:

Run a cycle consisting of any irreversible process, returning via a reversible process:

Consequence: Redraw system boundary to include immediate surroundings, so that Q = 0. For this new super system, then: %Stotal = %Ssystem + %Ssurr > 0 (equality for reversible processes) The entropy of the universe tends to a maximum. [Die entropie der welt strebt einen maximum zu. Clausius, 1850]

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Summary of First and Second Laws

First: dU = $Wad dU = $Q $W, or %U = Q12 W12 Second: dS = $Q/T dS > $Q/T, or dS = $Q/T + d&cycle - Note that the definition of T falls out of this:

Combined First and Second Laws: dU = $Q $W (always) $W = PdV (or other equivalent terms, depending on the nature of the system) dS = $Q/T dU = TdS PdV (Fundamental or characteristic equation tells all!) Reversible only? No always true because only state functions are involved.
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dU = TdS PdV TdS = dU + PdV U(S,V), or S(U,V), or V(S,U)] Compare to:

From characteristic equation, everything else can be constructed by taking derivatives. - Suppose that you could not you still could not make pmm, but then you could not use routine mathematical manipulations via state functions, which is what gives real analytical power to thermodynamics.

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Measurement of U and S Can only measure differences, %U and %S. (1)! Identify equilibrium states 1 and 2; (2)! Devise: (a) An adiabatic process between states 1 and 2. Measure or calculate W12(adiabatic) = %U (%H = %U + %PV) (b) A reversible process between states 1 and 2. Measure or calculate Q12 = %U W12 Then: 2 %S = '1 $Q12/T = Q12/T (if T = constant) Essentially all thermodynamic determinations of U and S reduce to this recipe - operational approach.
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dH = d(U + PV) = TdS PdV + PdV + VdP dH = TdS + VdP TdS = dH VdP H(S,P), or S(H,P), or V(S,P)] Compare to:

Integration of the TdS equations can be used to determine entropy changes from other changes in properties.

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Entropy Change of an Incompressible Substance Incompressible substance: Constant specific volume (density) and du depends only on temperature. Tds = du Pdv = du = c(T) dT ds = c(T) dT/T s2 s1 = '1 c(T) dT/T (incompressible, constant c).
2

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Entropy Change of an Ideal Gas For an ideal gas, du = cv(T) dT; dh = cP(T) dT; and Pv = RT ds = du/T + (P/T)dv ds = dh/T (v/T)dP ds = cv(T) dT/T + R dv/v; ds = cP(T) dT/T R dP/P s(T2,v2) s(T1,v1) = '1 cv(T) dT/T + R ln(v2/v1) s(T2,P2) s(T1,P1) = '1 cP(T) dT/T - R ln(P2/P1) Also: cP(T) - cv(T) = R T s ( 'T) cP(T) dT/T
2 2

(s are tabulated values of this integral; e.g., in Table A-22. Ideal gas properties of air.) 25