Physics 101: Lecture 31 Thermodynamics, part 2

Review of 1st law of thermodynamics 2nd Law of Thermodynamics Engines and Refrigerators The Carnot Cycle

Physics 101: Lecture 31, Pg 1

Quick Review
1st Law of Thermodynamics: energy conservation

Q = DU + W
Work done by (or on) system Increase (or decrease) in internal energy of system P Heat flow into (or out of) system U depends only on T (U = 3nRT/2 = 3PV/2) Point on P-V plot completely specifies state of system (PV = nRT) work done is area under curve for complete cycle

DU=0 Q=W
Physics 101: Lecture 31, Pg 2

Second Law of Thermodynamics

Not all processes that are allowed by energy conservation occur in nature. Why ? Example: Stone falls from height h: mgh -> m v2 (just before impact) -> heat (contact with floor) This process is consistent with energy conservation. The reversed process: Stone lying on floor cools down and moves upward to height h, has never been observed in nature, although it is also allowed by energy conservation: Q->1/2 mv2->mgh

Or: Ice melts but water does not spontaneously freeze, heat flows from hot to cold but never from cold to hot.

We need a new concept which makes these (reversed) processes highly unlikely.
Physics 101: Lecture 31, Pg 3

New concept: Entropy (S)

A measure of disorder or probability of state of a system. A property of a system (=state function, just like P, V, T, U)
related to number of different states of system

Examples of increasing entropy:

ice cube melts gases expand into vacuum

Change in entropy:

DS = Q/T (T in K !)

SI unit: [J/K]

>0 if heat flows into system (Q>0) <0 if heat flows out of system (Q<0)

Physics 101: Lecture 31, Pg 4

Reversible vs. Irreversible changes in a thermodynamic system:

"A transformation is said to be reversible when the successive states of the transformation differ by infinitesimals from equilibrium states. DSrev = 0

Reversible changes are conceived to be those that would occur very slowly, giving all the molecules in the system time to 'adjust' to new conditions, and all state variables time to adjust while still remaining uniform throughout a system. Theoretically you could imagine stopping at any point and reversing the change slowly, recovering the previous thermodynamic state. Definition given by Fermi (1936), in Thermodynamics:

Irreversible: Processes in which new entropy is created. A system spontaneously changes, or energy is transformed in a way that creates new entropy. This does not allow complete recovery of all aspects

of previous thermodynamic states.

DSirrev > 0

Processes that happen spontaneously are irreversible.

Physics 101: Lecture 31, Pg 5

1st and 2nd Law of Thermodynamics: A Perpetuum Mobile (perpetual motion) of 1st and 2nd kind is impossible.
Or: The energy of the universe is constant, the entropy of the universe seeks to be maximal. R.Clausius (1822-1888) Perpetuum Mobile of 1st kind : A machine that is able to provide useful work without input of external energy (e.g. heat) and without change of the physical or chemical status of its parts does not exist (or a machine that creates energy continuously does not exist). Perpetuum Mobile of 2nd kind: A machine undergoing a cyclic process which does nothing more than convert heat into mechanical (or other) work does not exist.
Physics 101: Lecture 31, Pg 6

M.C. Escher Waterfall (1961)

Second Law of Thermodynamics

The entropy change (Q/T) of the system+environment 0

never < 0 order to disorder

The entropy of the universe increases whenever an irreversible process occurs. All real processes in nature are irreversible.

Consequences:
A disordered state cannot spontaneously transform into an

more ordered state.

No engine operating between two reservoirs can be more

efficient than one that produces zero change in entropy. The latter is called a Carnot engine (no real engine can ever be perfectly reversible but Carnot is a useful idealization, since it represents the limiting case) .

Heat cannot be transferred spontaneously from cold to hot.

Physics 101: Lecture 31, Pg 7

Engines and Refrigerators

HEAT ENGINE
TH QH W QC QC TC system QH W REFRIGERATOR

TH

TC

System taken in closed cycle DUsystem = 0 Therefore, net heat absorbed = work done QH - QC = W (engine) QC - QH = -W (refrigerator) energy going into green blob = energy leaving green blob

Physics 101: Lecture 31, Pg 8

HEAT ENGINE

The objective: turn heat from hot reservoir (QH) into work The cost: heat is wasted

TH QH

1st Law: QH -QC = W

efficiency e W/QH
QC
TC

=W/QH
= (QH-QC)/QH = 1-QC/QH

Physics 101: Lecture 31, Pg 9

REFRIGERATOR

The objective: remove heat from cold reservoir (QC) The cost: work needs to be done

TH QH W QC TC

1st Law: QH = W + QC
coefficient of performance CPr QC/W

= QC/W
= QC/(QH - QC)

Physics 101: Lecture 31, Pg 10

Engines and the 2nd Law

The objective: turn heat from hot reservoir into work. The cost: heat is wasted

HEAT ENGINE TH QH

1st Law: QH -QC = W

efficiency e W/QH =W/QH = 1-QC/QH
QC

TC DS = QC/TC - QH/TH 0 DS = 0 for Carnot Therefore, QC/QH TC/ TH QC/QH = TC/ TH for Carnot Therefore e = 1 - QC/QH 1 - TC/ TH e = 1 - TC/ TH for Carnot => efficiency of a realistic engine can never be larger than eCarnot ! e largest if TC << TH

Physics 101: Lecture 31, Pg 11

Concept Question
Consider a hypothetical device that takes 1000 J of heat from a hot reservoir at 300K, ejects 200 J of heat to a cold reservoir at 100K, and produces 800 J of work. Does this device violate the first law of thermodynamics ? 1. Yes 2. No correct
This device doesn't violate the first law of thermodynamics because no energy is being created nor destroyed. All the energy is conserved.
W (800) = Qhot (1000) - Qcold (200) Efficiency = W/Qhot = 800/1000 = 80%

Physics 101: Lecture 31, Pg 12

Concept Question
Consider a hypothetical device that takes 1000 J of heat from a hot reservoir at 300K, ejects 200 J of heat to a cold reservoir at 100K, and produces 800 J of work. Does this device violate the second law of thermodynamics ? correct 1. Yes 2. No
W (800) = Qhot (1000) - Qcold (200) Efficiency = W/Qhot = 800/1000 = 80% Max eff = 1 - 100/300 = 67% = eCarnot

e > eCarnot is forbidden by second law : D S = DSH+DSC=200/100 J/K 1000/300 J/K < 0

Physics 101: Lecture 31, Pg 13

Concept Question
Consider a hypothetical refrigerator that takes 1000 J of heat from a cold reservoir at 100K and ejects 1200 J of heat to a hot reservoir at 300K. How much work does the refrigerator do? 2. What happens to the entropy of the universe? 3. Does this violate the 2nd law of thermodynamics?
1.

Answers: 200 J Decreases yes

TH QH W QC TC

QC = 1000 J QH = 1200 J

Since QC + W = QH, W = 200 J

DSH = QH/TH = (1200 J) / (300 K) = 4 J/K DSC = -QC/TC = (-1000 J) / (100 K) = -10 J/K DSTOTAL = DSH + DSC = -6 J/K decreases (violates 2nd law)

Physics 101: Lecture 31, Pg 14

Heat Capacities of an Ideal Gas

As discussed in Chapter 12, the heat needed to raise the temperature of a solid or liquid is given by: Q=cm DT where c is the heat capacity of the material.

Gases: Volume and/or pressure change when temperature changes (this effect can be safely neglected in case of solids and liquids). Heat capacity of a gas depends on if T changes at constant V, cV, or constant P, cP,: V=const.: DU=Q=cV m DT=3/2 n R DT => CV=cVm/n = 3/2 R P=const.: DU=Q-PDV=cP m DT-n R DT=3/2 n R DT => CP=cP m/n = 5/2 R CV and CP are the molar specific heat capacities of an ideal monatomic gas.
Physics 101: Lecture 31, Pg 15