Example 16-1B (page 631) For the reaction CO(g) + 2 H2(g) W CH3OH(g) equal concentrations of CO and CH3OH are

found at equilibrium. What is the equilibrium concentration of H2? (The value of Kc is given as 14.5.)

Kc =

[CH3OH] = 14.5 2 [CO][H2 ] 1 = 14.5 2 [H2 ]

[H2 ] = 1/ 14.5 = 0.263M

Example 16-2 (page 634) Consider the following reaction: N2(g) + 3 H2(g) W2 NH3(g), Kc = 3.6 X 108 (at 298K) What is the value of Kc for the following reaction at 298K? NH3(g) W N2(g) + 3/2 H2(g) when an equation is reversed, the new Kc is the reciprocal of the old Kc 2 NH3(g) W N2(g) + 3 H2(g) Kc = 1/Kc = 1/3.6 X 108 = 2.78 X 10-9 when an equation is multiplied by some factor, the new Kc is the old Kc raised to that power NH3(g) W N2(g) + 3/2 H2(g) Kc = (Kc) = (2.78 X 10-9) = 5.3 X 10-5

Example 16-3A (page 636) Consider the reaction: N2(g) + 3 H2(g) W2 NH3(g), Kc = 3.6 X 108 (at 298K) What is the value of Kp at 298K for the reaction? 2 NH3(g) WN2(g) + 3 H2(g) the value of Kc for this reaction (i.e. Kc) would be the reciprocal of the given value of Kc Kc = 1/Kc= 1/(3.6 X 108) = 2.78 X 10-9 now need to relate this to Kp
gas

in general, Kp = Kc(RT))n where R is the gas constant - since Kc is in M and Kp is in atm, must use 0.08206 L atm mol-1 K-1 )n = (moles of gaseous products) - moles of gaseous reactants) =4-2 =2 Therefore, Kp = (2.78 X 10-9)(0.08206X298)2 = 1.7 X 10-6
gas

Example 16-5A (page 641) For the reaction PCl5(g) W PCl3(g) + Cl2(g), Kc = 0.0454 at 261C A vessel is filled with these gases such that the initial concentrations of these gases are as follows: [PCl5] = 4.50 M, [PCl3] = 0.50 M, [Cl2] = 0.20 M In which direction will the net change occur?

[PCl3 ][Cl2 ] (0.50)(0.20) Qc = = = 0.022 [PCl5 ] (4.50)

i.e. Qc < Kc and therefore reaction will proceed to the right to form more products Example 16-7 (page 645) An equilibrium mixture of N2(g), H2(g), and NH3(g) is transferred from a 1.50 L flask to a 5.00 L flask. In which direction does the following reaction proceed: N2(g) + 3 H2(g) W2 NH3(g) when this gaseous mixture is transferred to a larger flask, the partial pressure of each gas decreases and the total pressure drops (note: total moles of gas remains the same but volume increases - P = nRT/V) the equilibrium will shift in such a way as to increase the total pressure (i.e. produce more moles of gas) the equilibrium will shift to the left (producing 4 moles of gas from 2 moles of gas)

Example 16-8 (page 645) Consider the reaction 2 SO2(g) + O2(g) W 2 SO3(g),

)H = -197.8 kJ

Will the amount of SO3(g) produced be greatest at high, or low temperatures? reaction is exothermic so reaction releases heat in the forward direction if this heat is consumed, that is, the mixture is cooled, the forward reaction would be favored the greatest amount of SO3(g) would be produced if the mixture was cooled

Example 16-9A (page 648) Consider the equilibrium 2 H2S(g) W 2 H2(g) + S2(g) When the equilibrium is reached in a 3.00 L flask at 1405 K, the following was found: Species H2S moles H2 S2

2.78 0.22 0.11

What is the value of Kc for this reaction?

[H2 ] 2 [S 2 ] (0.220 / 3.0) 2 (0.11/ 3.0) = 2.3X10 -4 Kc = = [H2 S] 2 (2.78 / 3.0) 2

Extra Exercise: What is Kp for this reaction?

Example 16-10A (page 649) An evacuated 5.00 L flask is filled with 1.86 moles of NOBr. It can react according to the reaction 2 NOBr(g) W 2 NO(g) + Br2(g) When equilibrium is established at 25C, there is 0.082 mol of Br2 present. What is the value of Kc, and Kp, for this reaction?
reaction: initial amts: changes: equilibrium amts: equilibrium concs: 2 NOBr(g) 1.860 mol -x 1.860 - 0.164 = 1.696 mol 1.696 mol/5.00 L = 0.3392 M
W

2 NO(g) +x 0.164 mol

Br2(g) 0.000 mol +x/2 = 0.082 mol x = 0.164 mol 0.082 mol 0.082 mol/5.00 L = 0.0164 M

0.000 mol

0.164 mol/5.00 L = 0.0328 M

[NO] 2 [Br2 ] (0.0328) 2 (0.0164 ) . Kc = = = 15 X10 -4 2 2 [NOBr ] ( 0.3392)

Kp = Kc(RT))n , )ngas = 3 - 2 =1
gas

Kp = (1.5 X 10-4)(0.08206 X 298) = 3.7 x 10-3

Example 16-11A (page 650) Sodium bicarbonate (baking soda) decomposes at elevated temperatures according to the following reaction: 2 NaHCO3(s) W Na2CO3(s) + H2O(g) + CO2(g) Kp = 0.231 at 100C What is the partial pressure of CO2(g) when this equilibrium is established starting with NaHCO3(s)? Kp = (PH2O)(PCO2) = 0.231 equal amounts of H2O(g) and CO2(g) are produced as NaHCO3(s) decomposes, therefore (PCO2)2 = 0.231, PCO2 = (0.231) = 0.481 atm

Example 16-12A (page 652) If 0.150 mol of H2(g) and 0.200 mol of I2(g) are introduced into a 15.0 L flask at 445C and allowed to come to equilibrium, how many moles of HI(g) will be present? H2(g) + I2(g) W 2 HI(g), Kc = 50.2 at 445 C
reaction: initial amts: changes: equilibrium amts: equilibrium concs: H2(g) -x 0.150 -x (0.150 -x)mol/15.0 L + I2(g) -x 0.200 - x (0.200 - x)mol/15.0 L
W

2 HI(g) 0.000 mol +2x 2x 2x mol/15.0 L

0.150 mol

0.200 mol

[HI]2 (2x /15)2 Kc = = [H2 ][I2 ] {(0.150 x) /15}{(0.200 x) /15} (2x)2 (1/15)2 x = (0.150 x)(0.200 x) (1/15)(1/15) (2x)2 = = 50.2 (0.150 x)(0.200 x)
need to solve this quadratic for x if we assume x<< 0.150, then 0.200 - x ~ 0.200 and 0.150 - x ~ 0.150

(2x)2 = 50.2 (0.150)(0.200) 4x 2 = (50.2)(0.150)(0.200) x = 0.614

clearly the assumption is NOT valid, so we cannot use it and the quadratic must be expanded and solved exactly (2x)2 = 50.2 (0.150 x)(0.200 x)

4x 2 = 50.2(0.150 x)(0.200 x) 4x 2 = 50.2x 2 50.2(0.150 + 0.200)x + 50.2(0.150)(0.200) 46.2x 2 17.57x + 1.506 = 0 for the general quadratic ax 2 + bx + c = 0, solve usin g b b2 4ac x= 2a 17.57 (17.57)2 4(46.2)(1.506) x= 2(46.2) x = 0.2498 or x = 0.1305
it is not physically possible for x to be 0.2498; x must be less than 0.150 since the reaction is limited by the amount of H2(g) initially present the only solution with physical significance is x = 0.1305 since moles of HI produced is equal to 2x, the moles of HI at equilibrium would be 2(0.1305) = 0.261 mol

Example 16-13A (page 653) Excess Ag(s) is added to 1.20 M Fe3+(aq). What are the equilibrium concentrations of the species in solution given that Ag+(aq) + Fe2+(aq) W Ag(s) + Fe3+(aq), Kc = 2.98

[Fe3 + ] = 2.98 Kc = + 2+ [Ag ][Fe ] (1.20 x) = 2.98 (x)(x)

could assume that x<<1.20 at this point to try to simplify solving for x, but you would find that the assumption is NOT valid - must solve quadratic exactly

1.20 x = 2.98x 2 2.98x 2 + x 1.20 = 0 1 12 4(2.98)( 1.20) x= 2(2.98) x = 0.4886 or x = 0.8242

a negative value for x has no physical meaning, so the only solution we can use is x = 0.4886 [Ag+] = [Fe2+] = 0.489M [Fe3+] = 1.20 - 0.4886 = 0.71 M