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Do Now:. Topic: Reaction Spontaneity. Spontaneous Processes. =physical or chemical change that occurs with no outside intervention However, some energy may be supplied to get process started = activation energy. Iron rusting 4Fe(s) + 3O 2 (g) 2Fe 2 O 3 (s) H = -1625 kJ.
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Do Now: Topic: Reaction Spontaneity
Spontaneous Processes =physical or chemical change that occurs with no outside intervention • However, some energy may be supplied to get process started = activation energy Iron rusting 4Fe(s) + 3O2(g) 2Fe2O3(s) H = -1625 kJ CombustionCH4(g) + 2O2(g) CO2(g)+ 2H2O(l) H = -891kJ
Because both reactions are spontaneous and exothermic, some 19th century scientist thought that all spontaneous reactions are exothermic…until they one day… H2O(s) H2O(l) endothermic
Some Spontaneous Processes are endothermic, some are exothermic • ΔH plays a role in determining whether a chemical process occurs spontaneously, but there is another piece to the puzzle. ENTROPY
Entropy, S • measure of disorder or randomness of particles in system • Law of Disorder (aka 2nd law of thermodynamics): spontaneous processes always occur in direction that increases chaos of system
Changes in Entropy,S S = Sfinal – Sinitial or Sproducts – Sreactants Spontaneous reactions need +S
Nature is lazy & disorganized • For system to lower energy: must release energy • nature favors exothermic processes with -H • Nature wants to increase S, so Sfinal > Sinitial • Nature wants S to be positive • But: • spontaneous endothermic processes can occur • so something(s) else important, too Low energy (- ΔH) Chaos (+ ΔS)
Affecting S • Changes in state • Sgas>Sliquid>Ssolid • Dissolving • CO2(g) CO2(aq)Sgas>SDissolved Gas • NaCl(S)NaCl(aq) SDissolved Solid>SSolid • SMixture>SPureSubstance • Entropy increases as you increase the number of gas molecules • 2SO3(g) 2SO2(g) + O2(g)S > 0 • Temperature • KE increases, Entropy increases
Predicting Entropy • Which has more entropy: • 1 mole dry ice [CO2(s)] • 1 mole CO2 gas 1 mole of CO2 gas • Which has more entropy: • 2 mole NaCl(s) • 1 mole NaCl(aq) • 1 mole NaCl(aq)
Predicting Spontaneity • Use Gibbs free energy expression G = H - TS • G = Free energy (available to do work) • H = enthalpy (heat) of reaction • T= temperature • S = change in entropy (disorder) • If G is (-) then rxn is spontaneous • If G is (+) then rxn is not spontaneous
G = H - TS Sometimes, more likely at high temp Never spontaneous Sometimes, more likely at low temp Always spontaneous If G is (-)then rxn isspontaneous IfG is (+)then rxn isnot spontaneous
Summary Nature is lazy and disorganized wants -H and +S Because the universe equals the system and the surrounding, spontaneous reactions will occur if -H and +S always
Entropy = 0? pure crystal with no imperfections at 0K • every atom is where it’s supposed to be • nothing is moving