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18 Pages

### Chapter_19[1]

Course: CHEM 113, Spring 2008
School: Scranton
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Word Count: 1191

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Describes Thermodynamics how energy is transferred or converted in chemical processes Energy conservation: the 1st law keeps track of energy transfer E=q+w E = total energy of a system q = heat flow w = work q &gt; 0 when heat flows into system q &lt; 0 when heat flows out of system w &gt; 0 when work is done on system w &lt; 0 when work is done by system 2nd law tells conditions...

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Describes Thermodynamics how energy is transferred or converted in chemical processes Energy conservation: the 1st law keeps track of energy transfer E=q+w E = total energy of a system q = heat flow w = work q > 0 when heat flows into system q < 0 when heat flows out of system w > 0 when work is done on system w < 0 when work is done by system 2nd law tells conditions needed for a change to be spontaneous Entropy (S) new state function Indicates the direction of a spontaneous change Spontaneity Spontaneous process = change in system occurs without impetus Nonspontaneous process = change will not occur without doing something to make it happen 1 Chemical Thermodynamics Difference between work and heat Heat Work Energy transferred into random motion Chemical Thermodynamics Energy transferred into orderly motion 2 Spontaneity & the 2nd law Universal observation that some things occur spontaneously & others do not Ball rolls downhill Tennis balls stop moving Beakers break NOTE a nonspontaneous change can happen if the system is changed. (a ball will roll uphill if it is pushed) What do spontaneous events have in common? Energy becomes randomized 2nd law: Energy will spontaneously move toward a more random distribution 3 Chemical Thermodynamics Entropy (S) Measure of how randomly energy is distributed S is larger when energy is more randomly distributed ice 0o C water 20o C Energy is not randomly distributed spontaneous Entropy increases Energy is randomly distributed An increase in entropy is often associated with disorder E.g. ice cube contains "ordered" molecules become disordered when melts Entropy depends upon both the system and the surroundings System = region of interest (e.g. ice cube) Surroundings = everything else (e.g. water, glass, table, etc...) Stot = Ssys + Ssur 4 Chemical Thermodynamics Effect of Ssys & Ssur Water becomes more ordered Ssur < 0 Salt becomes less ordered Ssys > 0 Dissolution is spontaneous: Stot > 0 Ssys > | Ssur| Entropy plays an important role in solubility Chemical Thermodynamics 5 2nd law of thermodynamics Stot > 0 for any spontaneous process Stot = Ssys + Ssur Ssys does not need to be positive for a spontaneous change (so long as Stot > 0) Spontaneous processes that create order: Freezing, protein folding, cell walls, etc... Occur spontaneously even though Ssys < 0 Because Stot > 0 due to entropy change of surroundings ( Ssur > 0) Stot > 0 when forward change is spontaneous Stot = 0 when no change is spontaneous Stot< 0 when reverse change is spontaneous Direction of spontaneity S = Sf Si (state function) S is related to heat and temperature Ssys = qrev/T system depends upon a "reversible" change Ssur = -qsys/T surroundings depends upon real heat that left system Chemical Thermodynamics Actual heat flow during the change 6 Molecular organization in a cell wall Molecular assembly is spontaneous because more disorder is created in the surroundings than order in the system Membrane forming molecule Imbedded protein Chemical Thermodynamics 7 Reversibility reversible process ice 0o C Add heat so slowly so that equilibrium is not disturbed water 0o C water 0o C equilibrium any step in melting can be exactly reversed irreversible process ice 0o C water 20o C water ~20o C Chemical Thermodynamics not in equilibrium cannot be exactly reversed since is never in equilibrium 8 Reversibility & entropy Reversible change Equilibrium exists throughout the change Process can be exactly reversed at any point during the change Ice/water at 0o C Irreversible change A change that removes system from equilibrium Cannot be reversed along same path A change can only be reversible if equilibrium exists throughout the change Entropy is defined as the change for a reversible path Even if the process is irreversible! energy Maximum change of any process is when the change is reversible qrev = maximum amount of energy to be randomized qrev qrev the actual amount of heat that is observed in the change Ssys = T 9 Chemical Thermodynamics Expansion of a gas into a vacuum Keep gas at constant T during expansion Open stopcock volume becomes 2x bigger Gas expands Stot > 0 E=q+w E = 0 (E only depends upon T) w = 0 (no work since doesn't push on surroundings) Ssur = 0 Ssys > 0 expansion is driven by increased disorder in gas (i.e. the system) q=0 So, qrev q since Stot > 0 Chemical Thermodynamics 10 Effect of temperature on entropy S increases with T Entropy of a pure substance For a pure substance: S (g) > S (l) > S (s) S of phase transitions At Tf: (s) & (l) in equilibrium (i.e. melting is reversible at Tf) qrev = Hf Sfus = Hfus/Tf At Tb: (l) & (g) in equilibrium qrev = Hvap Svap = Hvap/Tb Increasing disorder 11 Chemical Thermodynamics Standard molar entropies (So) Value of S per mole of substance in standard state at 1 atm. Bottom of entropy scale: (3rd law) So = 0 for substances at 0 K in a perfectly crystalline state Standard state state (s, l, g) of pure substance at 1 atm Trends: So (g) > So (l) > So (s) (with some exceptions) So generally increases with number of atoms in a molecule and molar mass Chemical Thermodynamics 12 Entropy changes in chemical reactions Standard entropy change of a reaction ( So) So = nSoproducts mSoreactants n, m = reaction stoichiometry 2 CH3OH (g) + 3 O2 (g) 2 CO2 (g) + 4 H2O (g) So = 2 SoCO2 + 4 SoH2O 2 SoCH3OH 3 SoO2 = 2(213.6 J mol-1K-1) + 4(188.83 J mol-1K-1) 2(237.6 J mol-1K-1) 3(205.0 J mol-1K-1) = 92.3 J mol-1K-1 Chemical Thermodynamics 13 Gibbs free energy (G = H TS) Predicts spontaneity of a chemical process, like Stot Because G is just another way of writing Stot Stot = Ssys + Ssur Ssur = -qsys - Hsys (because Hp = q) = T T Stot = Ssys Hsys T G = -T Stot = Hsys T Ssys constant P only For process: i f i f is spontaneous: Stot > 0 & G < 0 H is heat that leaves sysem f i is spontaneous: Stot < 0 & G > 0 Chemical Thermodynamics i f is at equilibrium: Stot = 0 & G = 0 14 Gibbs free energy Better than entropy don't need to calculate Ssys and Ssur G is determined from system's properties ( H, Ssys, T) Chemical reactions Will be spontaneous in the direction that minimizes Gibbs energy Gibbs energy determines position of equilibrium (K comes from G) Chemical Thermodynamics 15 Standard free energy of formation Standard free energy of formation ( Gfo) Go for the reaction that forms a compound from its elements with all species in their standard states Gfo = 0 for an element in its standard state Chemical reactions: Calculate Grxno from tables of Gfo Go = nGfoproducts mGforeactants 2 CH3OH (g) + 3 O2 (g) 2 CO2 (g) + 4 H2O (g) Grxno = 2 GfoCO2 + 4 GfoH2O 2 GfoCH3OH 3 GfoO2 = 2(-394.4 kJ/mol) + 4(-228.6 kJ/mol) 2(-161.9 kJ/mol) 3(0 kJ/mol) = -1380 kJ/mol Chemical Thermodynamics Rxn will spontaneously move to products since Grnxo < 0 16 Effect of temperature on spontaneity G = H T Ssys depends on T Increased T makes G smaller or more negative if Ssys > 0 i.e. increased T increases spontaneity e.g. solubility increases with T Whether G < 0 depends upon values of H, Ssys & T H + + Ssys + + T Ssys + + G + or + or + exothermic endothermic spon./non-spon. always spontaneous spontaneous at low T either either spontaneous at high T always nonspontaneous 17 Chemical Thermodynamics Free energy and equilibrium Gibbs free energy is related to equilibrium G = Go + RT lnQ for rxn in any state for rxn in standard state At equilibrium, Q = K & G = 0 = Go + RT lnK Go = -RT lnK Equilibrium constant can be calculated from standard free energy K = exp(- Go/RT) Chemical Thermodynamics 18
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