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Equilibrium. Equilibrium. Limiting reagent Concentrations become constant Dynamic situation Reversible reactions. 2NO 2 N 2 O 4. a. b. c. d. time. 2NO 2 N 2 O 4. Equilibrium Constant (K). represents a ratio of the concentrations of products to reactants at equilibrium:
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Equilibrium • Limiting reagent • Concentrations become constant • Dynamic situation • Reversible reactions
2NO2 N2O4 a b c d time
Equilibrium Constant (K) represents a ratio of the concentrations of products to reactants at equilibrium: aA +bB cC + dD
Equilibrium, or K, expression Equilibrium Constant (K) [C]c[D]d [A]a[B]b K=
Equilibrium Constant (K) • “[]” represents concentration in mol/L for (g) and (aq), only • Each “[]” must be raised to the power of its coefficient
Equilibrium Constant (K) • K < 1 indicates little product formation • K > 100 indicates great amount of product formation
Equilibrium Constant (K) • Write the K expression for the dimerization of nitrogen dioxide.
Equilibrium Constant (K) [N2O4] [NO2]2 What will the units of K be in this example? L/mol K=
Equilibrium Constant (K) • At 25°C, the equilibrium concentrations of NO2 and N2O4 are 0.0370M and 0.2315M. What is the value of K at this T?
Equilibrium Constant (K) [0.2315] [0.037]2 K= K=0.2315mol/L 0.001369mol2/L2 K=169 L/mol
N2 + 3H2 2NH3 • Write the K expression for the synthesis of ammonia.
Equilibrium Constant (K) [NH3]2 [N2][H2]3 What will the units of K be in this example? L2/mol2 K=
Equilibrium Constant (K) • At 300°C, the equilibrium concentrations are: [N2]eq= 2.59M [H2]eq=2.77M [NH3]eq=1.82M What is the value of K at this temperature?
Equilibrium Constant (K) [1.82]2 [2.59][2.77]3 K= K=3.3124mol2/L2 55.05mol4/L4 K=0.0602 L2/mol2
Equilibrium Constant (K) • Small K (<1) means… • Big K (>100) means… • Different manner of solving problems
Equilibrium Constant (K) • If a reaction is reversed, then the value of K for the reversed reaction is the reciprocal of K.
Equilibrium Constant (K) • So, if the dimerization of NO2 is reversed to be the decomposition of N2O4…
Equilibrium Constant (K) • K = (169 L/mol)-1 or 0.00592 mol/L
Equilibrium Constant (K) • At 25°C, the initial concentration of N2O4 is 0.750M. What are the eq. conc. of both species at this temperature?
Equilibrium Constant (K) • You will make an equilibrium chart to indicate the initial, change, and equilibrium concentrations.
[2x]2 [0.75] 0.00592= 4.44 x 10-3= 4x2 Equilibrium Constant (K) [2x]2 [0.75 – x] 0.00592=
0.0333= x Equilibrium Constant (K) 1.11 x 10-3= x2
Equilibrium Constant (K) 5% rule…is what you removed less than 5% of the smaller initial value?
Equilibrium Constant (K) If so, then your assumption that what you removed was so small it is negligible is correct
Equilibrium Constant (K) 5% rule test: 1x 1(0.0333) X 100 = 0.75 4.44% < 5%… assumption is good
Equilibrium Constant (K) Check your answer: [0.0666]2 [0.7167] K= 0.00619 K=
Equilibrium Constant (K) • At 25°C, the initial concentration of NO2 is 0.500M. What are the eq. conc. Of both species at this temperature? Remember that K = 169L/mol.
Equilibrium Constant (K) Since K is big, lots of product will be made. Thus, almost all of the initial amount of reactant will be used. You need to make two charts for a big K problem…Stoichiometry and Equilibrium
[0.25] 4x2 169= 676x2= 0.25 Equilibrium Constant (K) [0.25 - x] [2 x]2 169=
0.0192= x Equilibrium Constant (K) 3.70 x 10-4= x2
Equilibrium Constant (K) 5% rule test: 1x 1(0.0192) X 100 = 0.25 7.69% > 5%… assumption is bad
Equilibrium Constant (K) Since the assumption that x was so small it was negligible is bad, then you must re-insert x and solve the equation with x present.
[0.25 - x] 4x2 169= Equilibrium Constant (K) [0.25 - x] [2 x]2 169= 676x2= 0.25 - x
x = -b ± b2 – 4ac 2a Equilibrium Constant (K) 676x2 + x – 0.25 = 0 ax2 + bx + c = 0
Equilibrium Constant (K) You will get two values of x. If both are positive, then you will always select the smaller one. If one is positive and the other negative, you will select the positive one.
x = -1 ± 12 – 4(676)(-0.25) 2(676) x = -1 ± 1 – (-676) 1352 Equilibrium Constant (K)
x = -1 ± 677 1352 Equilibrium Constant (K) x = -1 ± 26.02 1352
Equilibrium Constant (K) x = 25.02 1352 = 0.0185 *accept this one OR x = -27.02 1352 = -0.0200