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10-end Expansion Work against CHANGING External Pressure A REVERSIBLE, ISOTHERMAL expansion: We gradually reduce Pext from Pinitial to Pfinal ; keep system at constant T (e.g., water bath) w = - nRT ln (Vfinal / Vinitial) whereR= 8.314 J/mol.K Comparing a REVERSIBLE vs. IRREVERSIBLE EXPANSION of a gas Reversibly: w = -nRT ln(Vf/Vi) Irreversibly against constant external pressure: w = -Pext V if a vaccum, then w = 0 = Free expansion Main Concept: Work done by the system via is LARGER (the value is more negative) for a REVERSIBLE process!! Second Concept: An ISOTHERMAL expansion (T = zero) ALSO has E = zero. This is because, for an ideal gas, internal energy is dependent ONLY on temperature, NOT P or V. Try it yourself: Two moles of an idea gas initially at 3atm and 183K are allowed to expand from 10L to 40L and a final pressure of 0.75 atm in two different ways: Find w, q and U. Path A. Isothermal, reversible expansion.

Path B. Cooled at constant volume (10L) until P = 0.75 atm and then allowed to expand against a constant pressure of 0.75atm until V = 40L, T=183K.

The Second Law of Thermodynamics In spontaneous changes the universe tends towards a state of greater entropy. A mirror shatters when dropped - does not reform. Its easy to scramble an egg - impossible to reverse! Food dye when dropped into water disperses Spontaneous processes are those which occur by themselves. Think of a spontaneous process as being feasable. Spontaneity has nothing to do with speed. What is Entropy? Entropy (S) is disorder, but on a molecular level. A jumbled sock drawer is a metaphor for disorder! thermal disorder: Add heat energy to a sample: molecules can occupy a more varied combination of translational, vibrational and rotational energy levels. positional disorder: Allow a sample to expand or mix with another material: molecules can occupy more physical locations. Boltzmann: Formal Definition of Entropy on a Molecular level microstate: exact translational, vibrational, rotational, potential energies of each particle in a system -or- one set of the possible positional arrangements of each particle in a system macrostate: overall SUM of these energies, or, total number of possible positional arrangements S = kB lnW

B

W = number of possible microstates of one molecule (positional and thermal -see later - we assume at T=0 you only have positional microstates) kB = Boltzman's constant = R/NA = 1.381 x 10-23 J molecule-1K-1 (NOTE: its PER MOLECULE!!)

B

Quantitative definition of Entropy Entropy is a state function, so S is path independent. When heat, q, is transferred into a system reversibly* at constant temperature: Units of S are J/K (for a specific amount) or, J/mol.K If S > 0 disorder increases If S < 0 disorder decreases *ie done slowly: surroundings stay at almost the same temperature

S = qrev / T

Entropy Changes in Changes of State Two possibilities: melting (fusion) or boiling (vaporization) Use S = qrev / T and note q = Hfus or Hvap . T will be either the melting point or boiling point (in K): Boiling point is that determined at 1atm. Sfus = Hfus / Tm.p. Svap = Hvap / Tb.p.

ALL S values for fusion and vaporization are POSITIVE: Solids are more ordered than liquids, which are more ordered than gases. The most ordered solids are crystals. Example: From tables, for acetone we have these values: Hvap = 29.1kJ/mol, BP = 329.4K. Find Svap.

Measuring Entropy We CAN assign an absolute zero value to Entropy: The Third Law of Thermodynamics states, The entropy of a pure, perfect, crystalline solid at 0 K is zero. Standard Molar Entropies, Smo are tabulated in Appendix. They are measured from graphs of (Cp/T) vs. T from almost zero K up to ~ 298K. Entropy Changes for Reactions: Entropy changes can be determined similarly to H for reactions (similar to Hess Law)

o S o = nS o 298 products nS reactants n n

S is << U or H:

3 NO (g ) N 2 O (g ) + NO 2(g )

One for you to try: calculate the entropy change for The value for N2O4 is 304.2 J./mol (answer: 175.8J/mol.K)

2 NO 2(g) N 2 O 4(g)

Entropy Change due to Temperature Change: Two types: S = n C ln (T2/T1) where C is CV,m or CP,m for ideal gas: read problem to see which C to use. S = m Cs ln (T2/T1) for a physical process not involving an ideal gas Example: We heat 20g of water from 25 to 35 C. What is the entropy change?

Entropy Change in Ideal Gas due to Isothermal Volume Change S = nR ln (V2/V1) R is 8.314 J/mol.K We can use Boyles Law to make an alternative version: S = nR ln (P1/P2) Example: Allow 30g of steam at 135 C to expand isothermally from 30L to 40L. What is the entropy change?

EXOTHERMIC vs ENDOTHERMIC PROCESSES AND SPONTANEITY Exothermic: system (the reaction) gives out heat to the surroundings: increases their entropy. Often spontaneous even if gases convert to solids! (heat must increase surrounding entropy enough to offset the loss of entropy in the system) How can an endothermic reaction be spontaneous? If reaction increases entropy enough to offset the loss in entropy of the surroundings! THE TOTAL ENTROPY IN THE UNIVERSE MUST INCREASE FOR ANY SPONTANEOUS PROCESS OVERALL ENTROPY CHANGE Stot = S + Ssurr NOTE: S is a STATE function so S for the system (not surroundings) is the same by any route! A process is spontaneous ONLY IF Stot is POSITIVE To find overall entropy change: 1. Find S using any of the previous equations 2. Find Ssurr using Ssurr = qsurr / T (assumes P,T of surroundings dont change) At constant pressure, q (system) = H(system) (calculate H(system) by methods shown in Ch.9 ) Since q (surroundings) = - q (system) we get: Ssurr = - H / T at constant T and P Entropy increase of surroundings gets bigger (process becomes more likely) as T decreases. Example: Lets use acetone again: Hvap = 29.1kJ/mol, BP = 329.4K What is Ssurroundings for condensation at the BP?

Example 2: Allow 30g of steam at 135 C to expand from 30L to 40L. Three routes: A: isothermal, reversible expansion B: isothermal free expansion* C: against a background pressure of 1atm* *irreversible. What is w,q, S, Ssurr, Stot? Which is/are spontaneous?

Equilibrium NO TENDENCY for process to occur - in EITHER direction Chemistry : DYNAMIC EQUILIBRIUM: Forward and Backward reactions STILL occur: BUT net result is no change in the amounts of products or reactants! AT EQUILIBRIUM: Stot = ZERO

GIBBS FREE ENERGY At constant pressure and temperature: Stot = S - H / T GIBBS FREE ENERGY is defined by: G = H -TS At constant pressure and temperature this means that G = - T Stot If G is negative free energy decreases - the reaction is spontaneous -FEASABLE!! INTERPRETING GIBBS FREE ENERGY The signs of H and S affect how the spontaneity of a reaction varies with temperature:

Hrxn and Srxn dont change greatly with T. Grxn is for the reaction at 298K . you can calculate Grxn at a nearby T using Hrxn and Srxn. It will be close.

AT EQUILIBRIUM G = ZERO

Example Calculate Gm for water melting at -10C, +10C and 0C and predict which is / are spontaneous. Assume Hfusion (= 6.01kJ/mol) and Sfusion ( = 22.0 J/K.mol) are independent of temperature.

Standard Gibbs Free Energy of Formation The standard reaction free energy per mole for the formation of one mole of the compound from its elements in their standard states. Its just like Hf! Can be used the same way! Gf of elements in their standard states are ZERO! A NEGATIVE value of Gf for a compound means that it is STABLE!! STANDARD REACTION FREE ENERGY We may find Grxn in several ways: If we have Hrxn and Srxn use: Grxn = Hrxn -TSrxn If we only have G values: use

o G o = nG o 298 products nG reactants n n

If we dont have Grxn or Hrxn and Srxn but we have S and H values: use:

o o H o = nHf products nHf reactants 298 n n o So = nSo 298 products nSreactants n n

Then: Grxn = Hrxn -TSrxn example 1: Heres a chemical reaction: Calculate G: 2Na(s) + 2H2O(l) 2NaOH(aq) + H2(g)

Example 2: Heres a famous chemical reaction: N2(g) + 3H2(g) 2NH3(g) Find Hrxn and Srxn comment on these and how G varies with temperature

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