Chapter 17 Free Energy and Thermodynamics
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1 Chapter 17 Free Energy and Thermodynamics
2 First Law of Thermodynamics! you can t win!! First Law of Thermodynamics: Energy cannot be Created or Destroyed!!the total energy of the universe cannot change!!though you can transfer it from one place to another!!e universe = 0 =!E system +!E surroundings
3 First Law of Thermodynamics! Conservation of Energy! For an exothermic reaction, lost heat from the system goes into the surroundings! two ways energy lost from a system,!!converted to heat, q!!used to do work, w! Energy conservation requires that the energy change in the system equal the heat released + work done!!!e = q + w!!!e =!H + P!V!!E is a state function!!internal energy change independent of how done
4 Limitations of the First Law of Thermodynamics!E = q + w! E universe = E system + E surroundings!e system = -!E surroundings!e system +!E surroundings = 0 =!E universe The total energy-mass of the universe is constant.! However, this does not tell us anything about the direction of change in the universe.
5 Thermodynamics and Spontaneity! thermodynamics predicts whether a process will proceed under the given conditions!!spontaneous process "!nonspontaneous processes require energy input to go! spontaneity is determined by comparing the free energy of the system before the reaction with the free energy of the system after reaction.!!if the system after reaction has less free energy than before the reaction, the reaction is thermodynamically favorable.! spontaneity! fast or slow
6 Comparing Potential Energy The direction of spontaneity can be determined by comparing the potential energy of the system at the start and the end.
7 Reversibility of Process! any spontaneous process is irreversible!!it will proceed in only one direction! a reversible process will proceed back and forth between the two end conditions!!equilibrium!!results in no change in free energy! if a process is spontaneous in one direction, it must be nonspontaneous in the opposite direction
8 Thermodynamics vs. Kinetics
9 Diamond! Graphite Graphite is more stable than diamond, so the conversion of diamond into graphite is spontaneous but don t worry, it s so slow that your ring won t turn into pencil lead in your lifetime (or through many of your generations).
10 Factors Affecting Whether a Reaction Is Spontaneous! The two factors that determine the thermodynamic favorability are the enthalpy and the entropy.! The enthalpy is a comparison of the bond energy of the reactants to the products.!!bond energy = amount needed to break a bond.!!!h! The entropy factors relates to the randomness/ orderliness of a system!!!s! The enthalpy factor is generally more important than the entropy factor
11 Enthalpy! related to the internal energy!!h generally kj/mol! stronger bonds = more stable molecules! if products more stable than reactants, energy released!!exothermic!!!h = negative! if reactants more stable than products, energy absorbed!!endothermic!!!h = positive! The enthalpy is favorable for exothermic reactions and unfavorable for endothermic reactions.! Hess Law!H rxn = "(!H prod ) - "(!H react )
12 A Spontaneous Endothermic Chemical Reaction. water Ba(OH). 2 8H 2 O(s) + 2NH 4 NO 3 (s) Ba 2+ (aq) + 2NO 3- (aq) + 2NH 3 (aq) + 10H 2 O(l)!H 0 rxn = kj
13 The Concept of Entropy (S) Entropy refers to the state of order. A change in order is a change in the number of ways of arranging the particles, and it is a key factor in determining the direction of a spontaneous process.! more order less order solid liquid gas more order crystal + liquid more order crystal + crystal less order ions in solution less order gases + ions in solution
14 Entropy! entropy is a thermodynamic function that increases as the number of energetically equivalent ways of arranging the components increases, S! S generally J/mol! S = k ln W!!k = Boltzmann Constant = 1.38 x J/K!!W is the number of energetically equivalent ways, unitless! Random systems require less energy than ordered systems
15 Changes in Entropy,!S! entropy change is favorable when the result is a more random system.!!!s is positive! Some changes that increase the entropy are:!!reactions whose products are in a more disordered state. "!(solid > liquid > gas)!!reactions which have larger numbers of product molecules than reactant molecules.!!increase in temperature!!solids dissociating into ions upon dissolving
16 The 2 nd Law of Thermodynamics! the total entropy change of the universe must be positive for a process to be spontaneous!!for reversible process!s univ = 0,!!for irreversible (spontaneous) process!s univ > 0!!S universe =!S system +!S surroundings! if the entropy of the system decreases, then the entropy of the surroundings must increase by a larger amount!!when!s system is negative,!s surroundings is positive! the increase in!s surroundings often comes from the heat released in an exothermic reaction
17 Entropy Change in State Change! when materials change state, the number of macrostates it can have changes as well!!for entropy: solid < liquid < gas!!because the degrees of freedom of motion increases solid! liquid! gas
18 Entropy Change and State Change
19 Entropy and Vibrational Motion. NO N 2 O 4 NO 2
20 Temperature Dependence of!s surroundings! when a system process is exothermic, it adds heat to the surroundings, increasing the entropy of the surroundings! when a system process is endothermic, it takes heat from the surroundings, decreasing the entropy of the surroundings! the amount the entropy of the surroundings changes depends on the temperature it is at originally!!the higher the original temperature, the less effect addition or removal of heat has
21 Gibbs Free Energy (G)!G, the change in the free energy of a system, is a measure of the spontaneity of the process and of the useful energy available from it.!g 0 system =!H0 system - T!S0 system!g < 0 for a spontaneous process!g > 0 for a nonspontaneous process!g = 0 for a process at equilibrium!g 0 rxn = " m!g0 products - " n!g0 reactants
22 Gibbs Free Energy,!G! maximum amount of energy from the system available to do work on the surroundings G = H T S!G sys =!H sys T!S sys "!G sys = T!S universe!g reaction = # n!g prod # n!g react! when!g < 0, there is a decrease in free energy of the system that is released into the surroundings; therefore a process will be spontaneous when!g is negative
23 Free Energy Change and Spontaneity
24 Gibbs Free Energy,!G! process will be spontaneous when!g is negative!!g will be negative when!!!h is negative and!s is positive "!exothermic and more random!!!h is negative and large and!s is negative but small!!!h is positive but small and!s is positive and large "!or high temperature!!g will be positive when!h is + and!s is!!!never spontaneous at any temperature! when!g = 0 the reaction is at equilibrium
25 !G,!H, and!s
26 The 3 rd Law of Thermodynamics Absolute Entropy! the absolute entropy of a substance is the amount of energy it has due to dispersion of energy through its particles! the 3 rd Law states that for a perfect crystal at absolute zero, the absolute entropy = 0 J/mol K!!therefore, every substance that is not a perfect crystal at absolute zero has some energy from entropy!!therefore, the absolute entropy of substances is always +
27 Standard Entropies! S! extensive! entropies for 1 mole at 298 K for a particular state, a particular allotrope, particular molecular complexity, a particular molar mass, and a particular degree of dissolution
28 Relative Standard Entropies States! the gas state has a larger entropy than the liquid state at a particular temperature! the liquid state has a larger entropy than the solid state at a particular temperature Substance S, (J/mol K) H 2 O (g) 70.0 H 2 O (l) 188.8
29 Relative Standard Entropies Molar Mass! the larger the molar mass, the larger the entropy! available energy states more closely spaced, allowing more dispersal of energy through the states
30 Relative Standard Entropies! the less constrained the structure of an allotrope is, the larger its entropy Allotropes
31 Relative Standard Entropies Molecular Complexity! larger, more complex molecules generally have larger entropy! more available energy states, allowing more dispersal of energy through the states Molar Substance Mass S, (J/mol K) Ar (g) NO (g)
32 Relative Standard Entropies Dissolution! dissolved solids generally have larger entropy! distributing particles throughout the mixture Substance S, (J/mol K) KClO 3 (s) KClO 3 (aq) 265.7
33 Calculating!G! at 25 C:!G o reaction = "ngo f (products) - "ngo f (reactants)! at temperatures other than 25 C:!!assuming the change in!h o reaction and!so reaction is negligible!g reaction =!H reaction T!S reaction
34 !G Relationships! if a reaction can be expressed as a series of reactions, the sum of the!g values of the individual reaction is the!g of the total reaction!!!g is a state function! if a reaction is reversed, the sign of its!g value reverses! if the amounts of materials is multiplied by a factor, the value of the!g is multiplied by the same factor!!the value of!g of a reaction is extensive
35 !G under Nonstandard Conditions "!!G =!G only when the reactants and products are in their standard states "!there normal state at that temperature "!partial pressure of gas = 1 atm "!concentration = 1 M "! under nonstandard conditions,!g =!G + RTlnQ "!Q is the reaction quotient "! at equilibrium!g = 0 "!!G =!RTlnK
36
37 The Relationship Between!G 0 and K at 25 0 C!G 0 (kj) K Significance x x10-18 Essentially no forward reaction; reverse reaction goes to completion x10-9 2x10-2 7x x10 1 6x10 8 3x x10 35 Forward and reverse reactions proceed to same extent FORWARD REACTION Forward reaction goes to completion; essentially no reverse reaction REVERSE REACTION
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39 Temperature Dependence of K! for an exothermic reaction, increasing the temperature decreases the value of the equilibrium constant! for an endothermic reaction, increasing the temperature increases the value of the equilibrium constant
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