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Entropy. Entropy. Entropy is defined as a state of disorder or randomness. In general the universe tends to move toward release of energy and greater entropy. 2. Entropy.
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Entropy Entropy is defined as a state of disorder or randomness. In general the universe tends to move toward release of energy and greater entropy. 2
Entropy The statistical interpretation of thermodynamics was pioneered by James Clerk Maxwell (1831–1879) and brought to fruition by the Austrian physicist Ludwig Boltzmann (1844–1906). 3
Entropy Spontaneous chemical processes often result in a final state is more Disordered or Random than the original. The Spontaneity of a chemical process is related to a change in randomness. Entropy is a thermodynamic property related to the degree of randomness or disorder in a system. Reaction of potassium metal with water. The products are more randomly distributed than the reactants 4
Entropy and Thermodynamics • According to the second law or thermodynamics the entropy of the universe is always increasing. • This is true because there are many more possibilities for disorder than for order.
Entropy Royal Flush Nothing hand
Entropy is Disorder Disorder in a system can take many forms. Each of the following represent an increase in disorder and therefore in entropy: • Mixing different types of particles. i.e. dissolving salt in water. • A change is state where the distance between particles increases. Evaporation of water. • Increased movement of particles. Increase in temperature. • Increasing numbers of particles. Ex. 2 KClO3 2 KCl + 3O2 7
Entropy States • The greatest increase in entropy is usually found when there is an increase of particles in the gaseous state. • The symbol for the change in disorder or entropy is given by the symbol, DS. • The more disordered a system becomes the more positive the value for DS will be. • Systems that become more ordered have negative DS values. 8
Entropy, S The entropy of a substance depends on its state: S (gases) > S (liquids) > S (solids) So (J/K-1mol-1) H2O (liquid) 69.95 H2O (gas) 188.8 9
Entropy and States of Matter S˚(Br2 liquid) < S˚(Br2 gas) S˚(H2O solid) < S˚(H2O liquid) 10
S increases slightly with T S increases a large amount with phase changes Entropy, Phase & Temperature 11
Entropy and Temperature The Entropy of a substance increases with temperature. Molecular motions of heptane at different temps. Molecular motions of heptane, C7H16 12
Entropy - Boltzman • Ludwig Boltzman S = k Ln W • Entropy is proportional to the number of degrees of freedom or possible configurations in a system. 13
Standard Entropy Values • The standard entropy, DSo, of a substance is the entropy change per mole that occurs when heating a substance from 0 K to the standard temperature of 298 K. • Unlike enthalpy, absolute entropy changes can be measured. • Like enthalpy, entropy is a state function. The change in entropy is the difference between the products and the reactants DSo = S So (products) - S So (reactants) 14
Standard Entropy Values Some standard enthalpy values • The amount of entropy in a pure substance depends on the temperature, pressure, and the number of molecules in the substance. • Values for the entropy of many substances at have been measured and tabulated. • The standard entropy is also measured at 298 K. 15
Spontaneity • A chemical reaction is spontaneous if it results in the system moving form a less stable to a more stable state. • Decreases in enthalpy and increases in entropy move a system to greater stability. • The combination of the enthalpy factor and the entropy factor can be expressed as the Gibbs Free Energy. 17
Gibbs Free Energy • The standard free energy change is defined by this equation DGo = DHo – T DSo Where DHo = the enthalpy change DSo = the entropy change T = Kelvin temperature • A chemical reaction is spontaneous if it results in a negative free energy change. 18
Gibbs Free Energy Possible Combinations for free energy change: DGo = DHo – T DSo 19
Free Energy Problem 1 • A certain chemical reaction is exothermic with a standard enthalpy of - 400 kJ mol-1. The entropy change for this reaction is +44 J mol-1 K-1. Calculate the free energy change for this reaction at 25 oC. Is the reaction spontaneous? Solution Convert the entropy value to kJ. 44 J mol-1 K-1 = 0.044 kJ mol-1 K-1 DG = - 400 kJ mol-1 – (298 K)(0.044 kJ mol-1 K-1) DG = - 400 kJ mol-1 – 13.1 kJ mol-1 DG = - 413.1 kJ mol-1 . Since DG is negative the reaction is spontaneous. Note. Because DH <0 and DS >0, this reaction is spontaneous at all temperatures. 20
Free Energy Problem 2 • A certain chemical reaction is endothermic with a standard enthalpy of +300 kJ mol-1. The entropy change for this reaction is +25 J mol-1 K-1. Calculate the free energy change for this reaction at 25 oC. Is the reaction spontaneous? Solution Convert the entropy value to kJ. 25 J mol-1 K-1 = 0.025 kJ mol-1 K-1 DG = + 300 kJ mol-1 – (298 K)(0.025 kJ mol-1 K-1) DG = + 300 kJ mol-1 – 7.45 kJ mol-1 DG =+ 292.55 kJ mol-1 . Since DG is positive the reaction is non-spontaneous. Note. Because DH >0 and DS >0, this reaction is non-spontaneous at low temperatures. It the temperature were substantially increased it would become spontaneous. 21