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Free Energy and Entropy
Some reactions which happen spontaneously are endothermic. The difference in enthalpy between the products and the reactants cannot be the only factor which decides if a chemical reaction takes place. It is often observed that reactions which occur spontaneously increase the randomness or disorder of a system   For example when an ionic crystal dissolves it passes from the regular arrangement of a crystalline lattice to a random solution of ions
This is termed an increase in entropy (disorder) of the system. The 2 factors, enthalpy and entropy,combine to give the  free energy  of the system  Free energy G = Enthalpy H – Temperature /K x Entropy S G = H - TS and  βˆ†G = βˆ†H - Tβˆ†S
For a chemical change to occur  βˆ†G must be negative . A change is therefore assisted by a decrease in enthalpy (βˆ†H negative) and an increase in entropy (βˆ†S positive) One method for finding the standard entropy change is to use  Standard entropy change = sum of standard entropies of products -  sum of standard entropies of reactants
Units:  entropy is measured in J K -1 mol -1 If a reaction has a positive entropy overall there is an increase in disorder. A negative entropy indicates a decrease in disorder.
Which of these processes lead to an increase in entropy? ,[object Object],[object Object],[object Object],[object Object],[object Object]
Calculate the standard entropy change for the reaction of chlorine and   ethene given the entropy values in   J K -1 mol -1 Cl 2   223.5  C 2 H 4  219  CH 2 ClCH 2 Cl  208  C 2 H 4  +  Cl 2  =  CH 2 ClCH 2 Cl Ξ”S = 208 – (219 + 223) = - 234  J K -1 mol -1 Lets consider if this is a sensible answer! We started with 2 molecules of reactants and ended with only 1 molecule of product. There is a decrease in disorder (or an increase in order) so the overall entropy change is negative.
Calculations on Gibbs Free Energy Using the equation  βˆ†G = βˆ†H – Tβˆ†S calculate the change in free energy for the following reaction   Fe 2 O 3(s)   +  3H 2(g)   ->  2Fe (s)   +  3H 2 O (g) and determine if it will take place at a) 20 o C and b) 500 o C Fe 2 O 3   H 2 Fe H 2 O (g) standard enthalpy  -822 0 0 -242 standard entropy  0.090 0.131  0.027  0.189 all values in kJ mol -1
βˆ† H = (3 x – 242 - ( -822) )  = + 96 kJ mol -1 βˆ†S = 3 x 0.189 + (2 x 0.027) – (3 x 0.131 + 0.090) βˆ†S = +0.138 kJ mol-1 a) at 20 0 C βˆ†G = βˆ†H - Tβˆ†S  βˆ†G = +96 – (20 +273) x 0.138 = +43.26 kJ mol -1 b) at 500 o C βˆ†G = +96 – (500 +273) X 0.138 = -10.7 kJ mol -1 The reaction will occur spontaneously at 500 o C (when βˆ†G is negative) but not at 20 o C

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12 Entropy

  • 1. Free Energy and Entropy
  • 2. Some reactions which happen spontaneously are endothermic. The difference in enthalpy between the products and the reactants cannot be the only factor which decides if a chemical reaction takes place. It is often observed that reactions which occur spontaneously increase the randomness or disorder of a system For example when an ionic crystal dissolves it passes from the regular arrangement of a crystalline lattice to a random solution of ions
  • 3. This is termed an increase in entropy (disorder) of the system. The 2 factors, enthalpy and entropy,combine to give the free energy of the system Free energy G = Enthalpy H – Temperature /K x Entropy S G = H - TS and βˆ†G = βˆ†H - Tβˆ†S
  • 4. For a chemical change to occur βˆ†G must be negative . A change is therefore assisted by a decrease in enthalpy (βˆ†H negative) and an increase in entropy (βˆ†S positive) One method for finding the standard entropy change is to use Standard entropy change = sum of standard entropies of products - sum of standard entropies of reactants
  • 5. Units: entropy is measured in J K -1 mol -1 If a reaction has a positive entropy overall there is an increase in disorder. A negative entropy indicates a decrease in disorder.
  • 6.
  • 7. Calculate the standard entropy change for the reaction of chlorine and ethene given the entropy values in J K -1 mol -1 Cl 2 223.5 C 2 H 4 219 CH 2 ClCH 2 Cl 208 C 2 H 4 + Cl 2 = CH 2 ClCH 2 Cl Ξ”S = 208 – (219 + 223) = - 234 J K -1 mol -1 Lets consider if this is a sensible answer! We started with 2 molecules of reactants and ended with only 1 molecule of product. There is a decrease in disorder (or an increase in order) so the overall entropy change is negative.
  • 8. Calculations on Gibbs Free Energy Using the equation βˆ†G = βˆ†H – Tβˆ†S calculate the change in free energy for the following reaction Fe 2 O 3(s) + 3H 2(g) -> 2Fe (s) + 3H 2 O (g) and determine if it will take place at a) 20 o C and b) 500 o C Fe 2 O 3 H 2 Fe H 2 O (g) standard enthalpy -822 0 0 -242 standard entropy 0.090 0.131 0.027 0.189 all values in kJ mol -1
  • 9. βˆ† H = (3 x – 242 - ( -822) ) = + 96 kJ mol -1 βˆ†S = 3 x 0.189 + (2 x 0.027) – (3 x 0.131 + 0.090) βˆ†S = +0.138 kJ mol-1 a) at 20 0 C βˆ†G = βˆ†H - Tβˆ†S  βˆ†G = +96 – (20 +273) x 0.138 = +43.26 kJ mol -1 b) at 500 o C βˆ†G = +96 – (500 +273) X 0.138 = -10.7 kJ mol -1 The reaction will occur spontaneously at 500 o C (when βˆ†G is negative) but not at 20 o C