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5.60 Thermodynamics & Kinetics

Spring 2008

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5. they cannot be circumvented.60 Spring 2008 Lecture #1 page 1 Thermodynamics Thermodynamics: → Describes macroscopic properties of equilibrium systems → Entirely Empirical → Built on 4 Laws and “simple” mathematics 0th Law ⇒ Defines Temperature (T) 1st Law ⇒ Defines Energy (U) 2nd Law ⇒ Defines Entropy (S) 3rd Law ⇒ Gives Numerical Value to Entropy These laws are UNIVERSALLY VALID. .

… • Knowledge if System is Homogeneous or Heterogeneous • Knowledge if System is in Equilibrium State • Knowledge of the number of components . but NOT mass • Isolated: Neither Mass nor Energy can transfer between the System and the Surroundings Describing systems requires: • A few macroscopic properties: p. m. n. V. T.60 Spring 2008 Lecture #1 page 2 Definitions: • System: The part of the Universe that we choose to study • Surroundings: The rest of the Universe • Boundary: The surface dividing the System from the Surroundings Systems can be: • Open: Mass and Energy can transfer between the System and the Surroundings • Closed: Energy can transfer between the System and the Surroundings.5.

V = . T) • Notation: or p = g(n. 5 Ar (s. 5 bar. T. p. T) 3 H2 (g. p. V.…) • Intensive: Independent of the size of the system V (T. all that is required is “n” and 2 variables. 50 K) . 1 bar. m.60 Spring 2008 Lecture #1 page 3 Two classes of Properties: • Extensive: Depend on the size of the system (n. All other properties then follow.…) [INDEPENDENT of the HISTORY of the SYSTEM] • For a one-component System. V. 100 °C) 3 moles (n=3) gas p=1 bar T=100 °C 2 Cl2 (g. 50 °C) .5.…) n The State of a System at Equilibrium: • Defined by the collection of all macroscopic properties that are described by State variables (p. 5 L. V. n. V = f (n.

5 bar.Reversible (always in Equilibrium) .60 Spring 2008 Lecture #1 page 4 Change of State: • Notation: (Transformations) 3 H2 (g.Adiabatic (no heat transfer between system and surroundings) .Constant Volume - - - . 50 °C) initial state final state • Path: Sequence of intermediate states 5 p (bar) 1 50 100 T (K) • Process: Describes the Path .5. 1 bar.Isobaric (constant pressure) .Irreversible (defines direction of time) .Isothermal (constant temperature) . 100 °C) = 3 H2 (g.

are in thermal equilibrium. heat flows from the warmer to the cooler object.60 Spring 2008 Lecture #1 page 5 Thermal Equilibrium (heat stops flowing) A B A B A B When a hot object is placed in thermal contact with a cold object. ≡≡≡≡≡ ZERO’th LAW of Thermodynamics ≡≡≡≡≡ If A B and and and B C C are in thermal equilibrium and are in thermal equilibrium. and at the same “temperature”. both bodies are said to have the same “temperature”. B .5. A . then A Consequence of the zero’th law: B acts like a thermometer. At this point. This continues until they are in thermal equilibrium (the heat flow stops). and C are all . This intuitively straightforward idea is formalized in the 0th Law of thermodynamics and is made practical through the development of thermometers and temperature scales.

15 -273.5.0036609 = 1/273.15 Note: 0 100 C (t = −273. . pts.15 °C is called the absolute zero.60 Spring 2008 Lecture #1 page 6 Operational definition of temperature (t) Need : (1) (2) (3) (4) substance property that depends on t reference points interpolation scheme between ref.15 °C ) is special t = −273. Based on Boyle’s Law lim pV p →0 ( ) t = constant = f (t ) depends on t for fixed t • the substance is a gas • f (t ) is the property • the boiling point (tb = 100°C ) and freezing point (tf = 0°C ) of water are the reference points • the interpolation is linear p 0 f(t)=f(0 C)(1+At) Experimental result: A = 0. Example: Ideal Gas Thermometer with the Celsius scale.

16= Ttp ⎡ lim pV ⎤ tp ⎥ ⎢ p →0 = T ⎢ 273.16K (triple point of H2O) p 0 f (T ) = f (Ttp ) 273.15 T = 0K corresponds to absolute zero (t = −273.5.60 Spring 2008 Lecture #1 page 7 ======= This suggests defining a new temperature scale (Kelvin) T (K ) = t ( °C ) + 273.16 or T lim pV p →0 ( ) T f(Ttp) 0 0 T(K) 273.16 ⎥ ⎢ ⎥ ⎣ ⎦ ( ) .15 °C ) ======= Better reference points used for the Kelvin scale today are T = 0K (absolute zero) and Ttp = 273.

31451 J R=⎢ ⎢ 273.16 ⎥ ⎢ ⎥ ⎣ ⎦ define ( ) valid for all gases for p → 0 the “gas constant” An ideal gas obeys the expression pV = RT at all pressures (⇒ the gas molecules do not interact) ⎡ lim ( pV ) ⎤ tp p→0 ⎥ = 8.T ) . p .60 Spring 2008 Lecture #1 page 8 Ideal Gases Boyle’s Law and the Kelvin scale lim pV p →0 ( ) T ⎡ lim pV ⎤ tp ⎥ ⎢ p →0 = T ≡ RT ⎢ 273.16 ⎥ K − mol ⎣ ⎦ (gas constant) The Ideal gas law pV = RT or pV = nRT This is an example of an equation of state V = f (n .5.

60 Spring 2008 Lecture #1 page 9 Equations of state IDEAL GAS LAW: pV = nRT → pV = RT Mixture of ideal gases comprising ni moles of each pi = p = pTotal = ∑ pi .5. i ni RT V Xi = Partial pressure of ith gas ni n mole fraction of ith gas Dalton’s Law pi = ni p = Xi p n Real Gases (a) -- do not necessarily obey ideal gas law Compressibility factor pV = ZRT Z= V ideal V real High T ⇒ Low T Repulsions dominate Attractions dominate Z>1 Z<1 Vreal > Videal Vreal < Videal ⇒ (b) Virial Expansion generally neglect B (T ) C ( ) T pV = Z (T ) = 1 + + +" RT V V 2 As p → 0. V → ∞. ⇒ ideal gas B = 0 ⇒ ideal gas (neglect C and higher order terms) .

60 Spring 2008 Lecture #1 page 10 (c) van der Waals Equation of state only two parameters.5. derived from molecular concepts • First assume “hard sphere” molecules pV = RT becomes p ( − b ) = RT V • Now put in attraction So ⎛ RT ⎞ p =⎜ ⎟ ⎝V − b ⎠ becomes ⎛ RT ⎞ a p =⎜ ⎟ − 2 ⎝V − b ⎠ V Rearranging ⇒ ⎛ p + a ⎞ V − b = RT ⎜ ⎟ V 2⎠ ⎝ ( ) .

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