1. Equilibrium Chapter 15

2. Equilibrium Have you ever tried to maintain your balance as you walked across a narrow ledge? Have you ever tried to maintain your balance as you walked across a narrow ledge? In a chemical reaction balance or equilibrium is also maintained. In a chemical reaction balance or equilibrium is also maintained. You can think of the yields  sign as the ledge You can think of the yields  sign as the ledge

3. Equilibrium systems exist in ocean water, blood, urine, and many other biological systems Chemical reactions for the most part are reversible You can think of the yield sign  as the ledge in a chem system

4. I. Chemical Equilibrium Concept Chemical Equilibrium occurs when opposing reactions are proceeding at equal rates Chemical Equilibrium occurs when opposing reactions are proceeding at equal rates At equil rate forward = rate reverse At equil rate forward = rate reverse A   B [] indicates a molar conc. A   B [] indicates a molar conc. Fr A  B rate kf [A] kf [A] = kr [B] Fr A  B rate kf [A] kf [A] = kr [B] Rr B  A rate kr [B] [B] = kf cons= Kc Rr B  A rate kr [B] [B] = kf cons= Kc Rearranging formula [A] kr Rearranging formula [A] kr

5. A dynamic equilibrium Individual molecules are undergoing change but there is no net exchange in the concentration of reactants and products Individual molecules are undergoing change but there is no net exchange in the concentration of reactants and products Does not mean that the concentrations are not changing just that the ratio equals a definite value Does not mean that the concentrations are not changing just that the ratio equals a definite value Look at Habber reaction figure 15.6 text. Look at Habber reaction figure 15.6 text. Dihydrogen monoxide: is also known as hydric acid, and is the major component of acid rain. contributes to the "greenhouse effect." may cause severe burns. contributes to the erosion of our natural landscape. accelerates corrosion and rusting of many metals. may cause electrical failures and decreased effectiveness of automobile brakes. has been found in excised tumors of terminal cancer patients.

6. Law of Mass Action Equilibrium can be reached from either direction Equilibrium can be reached from either direction Concentrations of reactants and products are expressed as Concentrations of reactants and products are expressed as aA + bB  pP + qQ aA + bB  pP + qQ equil constant Kc = [P] p [Q ] q products equil constant Kc = [P] p [Q ] q products [A] a [Q ] b reactants [A] a [Q ] b reactants

7. Equilibrium Constant mass action Kc depends on the stoichiometry not on mechanics Kc depends on the stoichiometry not on mechanics Doesn’t depend on the initial conc of reactants and products Doesn’t depend on the initial conc of reactants and products Doesn’t depend on other added sub as long as they do not react Doesn’t depend on other added sub as long as they do not react Varies with tempt Varies with tempt Catalyst do not effect just speeds – reaching eq. Catalyst do not effect just speeds – reaching eq.

8. Putting it Together Question? Main Ideas Details Monitor Monitor

9. Writing equilibrium expressions 2O 3 (g)  3O 2 (g) 2O 3 (g)  3O 2 (g) 2NO (g) + Cl 2 (g)  2NOCl (aq) 2NO (g) + Cl 2 (g)  2NOCl (aq) AgCl (s)  Ag + (aq) + Cl - (aq) AgCl (s)  Ag + (aq) + Cl - (aq) Kc = [O 2 ] 3 Kc = [NOCl] 2 [O 3 ] 2 [NO] 2 [Cl 2 ] [O 3 ] 2 [NO] 2 [Cl 2 ] Kc = [Ag + ] [Cl - ] Pure solids and liquids do not effect the equilibrium because their conc remain unchanged Pure solids and liquids do not effect the equilibrium because their conc remain unchanged

10. Eq expressed as pressure C 3 H 8(g) + O 2(g)  CO 2(g) + H 2 O (l) C 3 H 8(g) + O 2(g)  CO 2(g) + H 2 O (l) K p = CO 2p 3 K p = CO 2p 3 C 3 H 8p O 2p 5 C 3 H 8p O 2p 5 P = partial pressure of the gas P = partial pressure of the gas K p = k c (RT) delta n K p = k c (RT) delta n

11. What does kc tell you? Ex CO (g) + Cl 2 (g)  COCl 2 (g) Ex CO (g) + Cl 2 (g)  COCl 2 (g) Kc = [COCl 2 ] = 4.57 X 10^9 Kc = [COCl 2 ] = 4.57 X 10^9 [CO] [Cl 2 ] [CO] [Cl 2 ] Kc>>>1 larger numerator reaction goes almost totally to products – eq lies right – favors products Kc<<<1 larger denominator

12. Le Chatelier’s Principle If a system at eq is disturbed by a change in temperature, pressure, or the concentration of one of the components, the system will shift it’s eq pos so as to counter the effects of the distrubance If a system at eq is disturbed by a change in temperature, pressure, or the concentration of one of the components, the system will shift it’s eq pos so as to counter the effects of the distrubance Henri-Louis Le Chatelier (1858-1936)

13. Change in Concentration Le Châtelier's principle states that if the concentration of one of the components of the reaction (either product or reactant) is changed, the system will respond in such a way as to counteract the effect Le Châtelier's principle states that if the concentration of one of the components of the reaction (either product or reactant) is changed, the system will respond in such a way as to counteract the effect If a substance (either reactant or product) is removed from a system, the equilibrium will shift so as to produce more of that component (and once again achieve equilibrium) If a substance (either reactant or product) is removed from a system, the equilibrium will shift so as to produce more of that component (and once again achieve equilibrium)

14. Change in concentration If a substance (either reactant or product) is added to a system, the equilibrium will shift so as to consume more of that component (and once again achieve equilibrium) If a substance (either reactant or product) is added to a system, the equilibrium will shift so as to consume more of that component (and once again achieve equilibrium)

15. Putting it Together N 2(g) + 3H 2(g) 2NH 3(g) Question? Main Ideas Details Monitor Monitor How would inceasing H 2 change eq Predict the relative conc of each reactant and product

16. The reaction is driven "to the right" by the effects of added H 2 The reaction is driven "to the right" by the effects of added H 2 The eq conc’s will not be identical to the original state. However, Kc will be the same. The new equilibrium state contains a slightly higher concentration of NH 3 (g), and slightly lower concentration of N 2 (g) (as well as a slightly higher concentration of H 2 (g). The eq conc’s will not be identical to the original state. However, Kc will be the same. The new equilibrium state contains a slightly higher concentration of NH 3 (g), and slightly lower concentration of N 2 (g) (as well as a slightly higher concentration of H 2 (g).

17. Change in Volume and Pressure A chemical system in equilibrium can respond to the effects of pressure also. According to Le Châtelier's Rule, if the pressure is increased on a system, it will respond by trying to reduce the pressure. How does it do this? A chemical system in equilibrium can respond to the effects of pressure also. According to Le Châtelier's Rule, if the pressure is increased on a system, it will respond by trying to reduce the pressure. How does it do this? We are primarily concerned with homogeneous gaseous reactions We are primarily concerned with homogeneous gaseous reactions The stoichiometry of the reaction may lead to a greater number of molecules on one side of the equation. The stoichiometry of the reaction may lead to a greater number of molecules on one side of the equation. For example, in the Haber reaction, N 2(g) + 3H 2(g) 2NH 3(g) there are twice as many moles of reactants as products For example, in the Haber reaction, N 2(g) + 3H 2(g) 2NH 3(g) there are twice as many moles of reactants as products

18. If the Haber reaction were in equilibrium, and the pressure was increased, the reaction would respond to oppose the increase in pressure. It could accomplish this by shifting the equilibrium to the right (producing NH3(g)) If the Haber reaction were in equilibrium, and the pressure was increased, the reaction would respond to oppose the increase in pressure. It could accomplish this by shifting the equilibrium to the right (producing NH3(g)) This would reduce the overall number of moles in the reaction, and therefore, lower the pressure This would reduce the overall number of moles in the reaction, and therefore, lower the pressure Systems shift to the side with the fewest number of moles if both are the same then no change in eq con’s occurs Systems shift to the side with the fewest number of moles if both are the same then no change in eq con’s occurs

19. Changes in Temperature The intrinsic value of K does not change when we increase concentrations or pressures of components in a reaction. However, almost every equilibrium constant (K) changes in response to changes in temperature. The intrinsic value of K does not change when we increase concentrations or pressures of components in a reaction. However, almost every equilibrium constant (K) changes in response to changes in temperature. We will consider reaction conditions under which no work is done, and therefore all energy changes associated with reactions will be manifested by temperature changes) We will consider reaction conditions under which no work is done, and therefore all energy changes associated with reactions will be manifested by temperature changes)

20. Temperature Changes Exothermic reactions are associated with heat release when the reaction proceeds in the forward direction Exothermic reactions are associated with heat release when the reaction proceeds in the forward direction Endothermic reactions are associated with heat release when the reaction proceeds in the reverse direction (i.e. heat is absorbed in the forward direction) Endothermic reactions are associated with heat release when the reaction proceeds in the reverse direction (i.e. heat is absorbed in the forward direction)

21. These two types of reactions and their associated heat changes can be written as: These two types of reactions and their associated heat changes can be written as: Exothermic: Reactants yield Products + Heat Exothermic: Reactants yield Products + Heat Endothermic: Reactants + Heat yield Products Endothermic: Reactants + Heat yield Products If temperature is increased, the equilibrium will shift so as to minimize the effect of the added heat If temperature is increased, the equilibrium will shift so as to minimize the effect of the added heat The reaction will shift in the appropriate direction such that the added heat is absorbed The reaction will shift in the appropriate direction such that the added heat is absorbed

22. When heat is added to exothermic reactions at equilibrium, products will be consumed to produce reactants (shift to the LEFT) May also be written delta t is negative. When heat is added to exothermic reactions at equilibrium, products will be consumed to produce reactants (shift to the LEFT) May also be written delta t is negative. When heat is added to endothermic reactions at equilibrium, reactants will be consumed to produce products (shift to the RIGHT) May also be written delta t is positive. When heat is added to endothermic reactions at equilibrium, reactants will be consumed to produce products (shift to the RIGHT) May also be written delta t is positive.

23. Based on this behavior, what is the effect of T upon K? Assume K = 1.0 for an exothermic reaction at equilibrium. Assume K = 1.0 for an exothermic reaction at equilibrium. Added heat causes the reaction to shift to the left. Reactants <= Products + Heat Added heat causes the reaction to shift to the left. Reactants <= Products + Heat Thus, 1.0 must represent a reaction quotient, Q, that is too large in comparison to the new value of K. Thus, 1.0 must represent a reaction quotient, Q, that is too large in comparison to the new value of K. Thus, the effect of increasing temperature on an exothermic reaction is to lower the value of K. Thus, the effect of increasing temperature on an exothermic reaction is to lower the value of K. Conversely, the effect of increasing temperature on an endothermic reaction is to increase the value of K Conversely, the effect of increasing temperature on an endothermic reaction is to increase the value of K

24. Putting it Together Calc Delta H of formation for C 3 H 8(g) + O 2(g)  CO 2(g) + H 2 O (l) Question? Is the value Exo,or endotherm Main Ideas Details Monitor Monitor How would inc. temp effect eq How would dec temp eff eq k

25. Calculations with eq K Example calculating unknown concentrations using the eq constant Example calculating unknown concentrations using the eq constant CO (g) + 3H 2(g) CH 4(g) + H 2 0 (g) CO (g) + 3H 2(g) CH 4(g) + H 2 0 (g) At eq 0.3 mol of CO, 0.1 mol H 2 and 0.02 mol of H 2 0 are in 1.0 liter of a vessel at 1200 k kC is 3.92 what is the conc of CH 4 ? At eq 0.3 mol of CO, 0.1 mol H 2 and 0.02 mol of H 2 0 are in 1.0 liter of a vessel at 1200 k kC is 3.92 what is the conc of CH 4 ?

26. Kc = [CH 4 ] [H 2 O] Kc = [CH 4 ] [H 2 O] [CO] [H 2 ] 3 [CO] [H 2 ] 3 3.93 = [CH 4 ] (.020) (0.30) (0.10) 3 (0.30) (0.10) 3 [CH4] = (0.30)(0.10) 3 3.93 (0.020) (0.020) 0.059 mol/l

27. Learning Check PCl 5(g) PCl 3(g) + Cl 2(g) A l.0 liter vessel has a unknown amount of PCl 5 at eq Kc at 250 0 C is 0.0415. Calc the unknow conc. if 0.02moles of PCl 3 and Cl 2 are in the container. (0.0096) A l.0 liter vessel has a unknown amount of PCl 5 at eq Kc at 250 0 C is 0.0415. Calc the unknow conc. if 0.02moles of PCl 3 and Cl 2 are in the container. (0.0096)

28. Solving linear eq equasions CO(g) + H20(g) C02(g) + H2(g) CO(g) + H20(g) C02(g) + H2(g) Given 1.0 mol of CO 2 and H 2 0 in a 50.0 l vessel. How many moles are in an eq mix at 1000 o C Ec = 0.58 at 1000 o C Given 1.0 mol of CO 2 and H 2 0 in a 50.0 l vessel. How many moles are in an eq mix at 1000 o C Ec = 0.58 at 1000 o C CO(g) + H 2 0(g) C0 2 (g) + H 2 (g CO(g) + H 2 0(g) C0 2 (g) + H 2 (g I 0.02 0.02 0 0 C -x -x +x +x E 0.02-x 0.02-x x x

29. 0.58 = [CO 2 ][H 2 ] = X 2 0.58 = [CO 2 ][H 2 ] = X 2 [CO] [H 2 O] (0.02-X) 2 [CO] [H 2 O] (0.02-X) 2 +,- 0.76 = X 2 +,- 0.76 = X 2 (0.02-X) (0.02-X) (the neg one gives a neg answer x can’t be neg) (the neg one gives a neg answer x can’t be neg) _ +0.76(0.02-X)=X 0.0152-0.76X=X 0.0152-0.76X=X 0.0152= 1.76X 0.0152= 1.76X X= 0.0086 X= 0.0086

30. H 2(g) + I 2(g) 2HI (g) What is the eq comp of a reaction mixture starting with 0.500 mol each of H 2 and I 2 in a 1 l vessel? Kc = 49.7 at 458 o C (H 2 &I 2 = 0.11 mol/l HI = 0.78 mol/l What is the eq comp of a reaction mixture starting with 0.500 mol each of H 2 and I 2 in a 1 l vessel? Kc = 49.7 at 458 o C (H 2 &I 2 = 0.11 mol/l HI = 0.78 mol/l

31. Equil with quadratic expressions Calc the conc. of the previous problem with 1.00 molar H2 and 2.00 molar I2 as the starting concentrations. Calc the conc. of the previous problem with 1.00 molar H2 and 2.00 molar I2 as the starting concentrations. H 2(g) + I 2(g) 2HI (g) H 2(g) + I 2(g) 2HI (g) I 1.00 2.00 0 C -x -x 2x 49.9 = (2x) 2 E 1.00-x 2.00-x 2x (1.00-x)(2.00-x)

32. (1.00-x)(2.00-x)= (2x)2 (1.00-x)(2.00-x)= (2x)2 49 49