Books: H. C. Van Ness, "Understanding Thermodynamics" H. C.

Von Baeyer, "Why Warmth Disperses and Time Passes" Photocopies are available at Copy Central (opposite North Gate of campus) for ~ $15 for the two.
Reference Texts: (on reserve in Engineering Library) Van Wylen, Sonntag, and Borgnakke, Fundamentals of Classical Thermodynamics, 4th Ed., Wiley (1994) Gaskell, Introduction to Metallurgical Thermodynamics Ed., McGraw-Hill (1981);

, 2nd

Assignment #1: Read Von Baeyer; solve problem on slide 6 Quiz 9/5 AM (closed book) will cover V-B and lecture on History of Thermo 1

8/28/07

A Brief History of Thermodynamics

The driving force for the development of thermodynamics was the invention of the steam engine at about 1700 From 1700 to 1900, thermodynamic theory was slowly and painfully developed By 1900, classical thermodynamics was essentially complete In time, various special branches of thermodynamics developed
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The Concept of Temperature

Without realizing its significance, Galileo (ca 1630) developed a crude thermometer

Fahrenheit (1715); measured temperature by expansion of a fluid (mercury) Celsius (1742) defined 0oC as the melting point of ice; 100oC as the boiling point of water; with a scale in between linear with expansion of fluid why?
Lavoisier (1780) realized that matter is composed of discrete atoms and molecules Dalton (1808), temperature interpreted as a measure of particle speed (gas) or vibration (solid) 3

Kelvin (ca 1885) introduced the notion of the absolute zero temperature, where all atomic motion stops: T(K) = T(oC ) + T0; absolute zero is 0 K or -T0oC . How to determine T0 ?
T,oC
Solid Ice CO2 x x -273=T0

Boiling water X

0 Absolute zero = - 273 oC

pgas

Gas Thermometer
Air in the flask expands with temperature and exerts pressure on the surface of the oil, causing it to rise in the column. with ice in the air flask: TF = 0 + 273 = 273 K - Relief valve open - po = 1 atm

Column Area = AC

~ 1.6 m

- moles gas = (p o / R)VF / TF Vt / To

To = 22 + 273 = 295 K

Tubing, vol = Vt

Relief valve

n1
Reservoir Flask Vol = VF Oil 5

Heater

 Relief value closed & ice removed air flask at room temperature (22 oC) oil rises to height h1 Homework problem! solve for h1
repeat

pC

for flask at T = 100oC g = 9.8 m/s2

h1

roil = 0.84 g/cm3 Volumes:

- Air flask 500 cm3

- Tubing from air flask to oil flask: 2 cm3 - Oil flask neck inside diam. = 3 cm - Column inside diameter 0.95 cm
6

Initial oil level

p1

Finally, the temperature scales are fixed: International Committee (1954): defines the unique state of water: the triple point where ice, water, and water vapor (only) coexist at 0.01oC and 611 Pa (0.00611 atm) The triple-point temperature anchors the temperature scale Does not affect absolute zero (-273.15oC)
7

Heat
Since the 18th Cent., heat was viewed as a fluid (caloric) that moves from a body at high temperature to one at low temperature During the 19th Cent., the correct view of heat was uncovered:

Heat is energy in motion from a hot system to cold surroundings (or vice versa)
Some effects of heat : -increasing the temp.of a body - melting a body - vaporizing a liquid - producing mechanical work
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Work
Known from mechanics since Newton (1687) as force x distance. Heat and Work are two aspects of energy in motion; work is completely convertible to heat (Rumford, Joule (1840))

but not vice versa! (e.g., steam engine)

Forms of Work: expansion/contraction: like a balloon rotating equipment: steam or gas turbine electrical work: electric cars mechanical: moving levers, lifting weights, etc.

Count Rumfords canon-boring experiment (1797)

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The Mechanical Equivalent of Heat

Joule (ca 1850) the first thermodynamic experimentalist measured: - heat in calories (to raise the temp. of 1 gram of water 1oC) - work in Joules (force of 1 Newton over 1 m)

4.184 Joules per calorie

With energy, heat and work in the same units the 1st law was ready to be established
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But what is energy?

We have no knowledge of what energy is it is an abstract thing (Richard Feynman)

Energy comes in many interconvertible forms: - internal (atomic motion in solids, liquids & gases) - electrical & magnetic
- surface
- chemical - in molecular bonds (coal power) - kinetic (wind power)

- potential gravitational (hydropower)

- radiant (solar power) - nuclear in proton-neutron bonds (nuclear power)
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Energy and the First Law

energy cannot be created or destroyed:

conservation of energy - Mayer (1842) - Helmholz, Clausius, (ca 1850) energy is related to heat and work by the 1st Law of Thermodynamics

Energy is a property of a body; heat and work are not

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The Second Law

Development of steam engines (Watt 1778) showed empirically that heat cannot be completely converted to work Carnot (1824) showed theoretically why this is so proposed the concept of the reversible processes For an engine (of any kind) to produce work, hot and cold reservoirs are required to provide high-quality heat and receive reject low-quality heat practical cycles for producing work are developed (Rankine, Otto, Brayton) 19th Cent.
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Entropy and the 2nd Law

Qualitative statements:

Clausius: It is impossible to convert heat completely to work

Kelvin Planck: It is impossible for any any engine to transfer heat from a cold source to a hot source without work being done By analyzing many experiments and processes involving transfer of heat, Clausius (ca 1850) uncovers a new thermodynamic property, which he names entropy - related to the heat exchanged between system and surroundings - not related to work - places 2nd law in quantitative form
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Chemical/Materials Thermodynamics
This branch deals with: - multiple components, multiple phases - chemically reacting mixtures - equilibrium at conditions of fixed p and T Developed by Willard Gibbs (Yale Univ. 1890) Gibbs introduces the chemical potential the driving force for:

- Chemical reactions - Exchange of a species between phases - Diffusion of a species in a single phase

At equilibrium, these processes STOP

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Statistical Thermodynamics
Links atomic motions to thermodynamic properties Boltzmann (ca 1885) discovers the formula for the absolute entropy Planck (~ 1900) quantization of energy states Einstein, Debye (1905) quantum mechanical explanation of specific heats of solids Fermi, Dirac, Bose quantum statistical thermodynamics Giauque (1930, UCB)- the 3rd Law: The entropy of a body is zero at 0 K
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