Chapter 14

Chemical Equilibrium
“Old Chemists Never Die; they just reach
EQUILIBRIUM!”

All physical and chemical changes TEND toward a
state of equilibrium.

A (l) A (g)
A (s) A (l)

Dynamic Equilibrium
The net result of a dynamic equilibrium is that no
change in the system is evident.
Le Chatelier’s Principle - If a change is made in a
system at equilibrium, the equilibrium will shift in such
a way so as to reduce the effect of the change.
Apply
Pressure

Pressure applied to the system at equilibrium caused it to
shift until a new equilibrium was established.
02/26/17 2

Dynamic Equilibrium

Open System
Evaporation (No Equilibrium)

Evaporation

Liquid Gas Liquid Gas Liquid Gas
(No Equilibrium) (No Equilibrium) (Equilibrium)
02/26/17 3

Ag + Equilibrium AgCl (s) Rate of Precipitation = Rate of Dissolving HC2H3O2 (aq) H + + C2H3O2 - Rate of dissociation (ionization) = Rate of Association HC2H3O2 H+ H + C2H3O2 - C2H3O2 - HC2H3O2 02/26/17 4 . Dynamic Equilibrium Ag + + Cl . AgCl (s) Ag + Cl - Chemical Cl .

+ 6 H2O (l) Co(H2O)62+ + 4 Cl- White Colorless Solution NH4Cl (s) NH 4+ + Cl- You can actually “see” the equilibrium shift! 02/26/17 5 . CHEM 1108 Lab Experiment Orange Red HC2H3O2 H+ + C2H3O2- Blue Pink [CoCl4]2.

Reversible Reactions R1 N2O4 (g) 2 NO2 (g) R2 2 NO2 (g) N2O4 (g) R1 N2O4 (g) 2 NO2 (g) [R1 = R2] R2 02/26/17 Homogeneous Equilibrium 6 .

0150 M 0.0146 M 0. Reversible Reactions [N2O4]i [NO2]i [N2O4]eq [NO2]eq Exp. 3 0.0125 M 0.009 66 M Exp. 1 0.0250 M 0.0250 M 0.006 54 M N2O4 (g) 2 NO2 (g) Reaction Quotient Equilibrium Constant QC = [NO2]2 KC = [NO2]2eq [N2O4] [N2O4]eq 02/26/17 7 . 2 0.0 M 0.0923 M 0.008 23 M Exp.0 M 0.0202 M 0.

the system is “at equil- ibrium” and the reaction quotient = equilibrium constant.0202] = 0.004 63 M aA + bB cC + dD KC = [C]c[D]d 02/26/17 8 [A]a[B]b .009 23] = 0.008 23]2/[0.004 62 M Experiment 2 KC = [0.006 54]2/[0.When the rates of the forward and reverse reactions are equal. Experiment 1 KC = [0.009 66]2/[0.004 64 M Experiment 3 KC = [0. Equilibrium Constants Equilibrium Constant .0146] = 0.

51 5 0.00171 0. Equilibrium Constants H2 (g) + I2 (g) 2 HI (g) QC = [HI] 2 KC = [HI]2eq [H2][I2] [H2]eq[I2]eq Exp.01767 54.01648 54.58 02/26/17 Median KC = 54.47 9 .00114 0.00050 0.00114 0.00841 54.62 3 0.58 2 0. [H2]eq [I2]eq [HI]eq KC 1 0.00291 0.00366 53.01559 54.42 6 0.00356 0.00183 0.00313 0.00234 0.93 4 0.00225 0.00125 0.01685 53.00050 0.

Equilibrium Constants 4 NH3 (g) + 3 O2 (g) 2 N2 (g) + 6 H2O (g) QC = [N2]2[H2O]6 [NH3]4[O2]3 KC = [N2]eq2[H2O]6 [NH3]eq4[O2]eq3 02/26/17 10 .

2 O3 (g) = 3 O2 (g)? 02/26/17 11 .The concentration of N2O4 = concentration of NO2 = 0. The equilibrium constant for N2O4 (g) = 2 NO2 (g) is 0. Class Problem 14.1 . Reaction Quotient vs. Calculate QC and state which direction the reaction will go.0125 M in a reaction vessel. what is the value of the KC for the equilibrium.0 x 10-8 M.If [O2] = 0.21 M and [O3] = 6.004 63. Equilibrium Constant Class Problem 14.2 .

These reactions occur at the interface between phases . it can be considered a part of the equilibrium constant and. thus. C (s. the concentration of a solid or liquid component remains constant in a heterogeneous equilibrium.on the surface of liquids and solids. does NOT appear in the KC expression. graphite) + CO2 (g) = 2 CO (g) KC = [CO]2 Keq = [CO]2 02/26/17 [C][CO2] 12 . At a constant temperature. WHY? Since the concentration is constant.A reaction that takes place in more than one phase or state. Chemical Equilibrium Heterogeneous Reaction .

004 78 .012 50 M in I2 (g). M .000 00 Change (C) in conc.005 00 0.A mixture that was initially 0.000 22 0.012 50 0. and contained no HI (g).007 72 M. The resulting equilibrium concentration of I2 (g) was found to be 0. M . Chemical Equilibrium Class Problem 14.0..0. What is the value of the KC for this equilibrium at 425.009 56 Equil.4oC Equation: H2 (g) + I2 (g)  2 HI (g) Initial (I) conc.007 72 + 0..0.4oC until equilibrium was reached. (E) conc.005 00 M in H2 (g) and 0. was heated at 425.004 78 + 0.4oC? Construct an “ICE” Table: 425.009 56 02/26/17 13 ..3 . M 0.

007 72) Class Problem 14.000 mol each of H2O (g) and CO (g) are introduced into an empty 1.009 56)2 KC = = [H ][I ] = 54 2 2 (0.When 1.000 L vessel at 959 K and allowed to come to equilibrium. Chemical Equilibrium Calculate KC: [HI]2 (0. the equilibrium mixture contains 0. Find KC for H2O (g) + CO (g)  H2 (g) + CO2 (g) Construct an “ICE” Table: 02/26/17 14 . .422 mol H2O (g).4a.000 22) (0.

.000 1.00 M and [CO]I = 4. Chemical Equilibrium 959oC Equation: H2O (g) + CO (g)  H2 (g) + CO2 (g) I 1.0.578 [H2][CO2] (0.000 0.422 0.0.4b.422)2 Class Problem 14.000 C .Suppose that [H2O]I = 2.00 M? What are the equilibrium concentrations of the four species? 02/26/17 15 .578 E 0.000 0.422 0.578 .578 + 0.88 [H2O][CO] (0.578 + 0.578 0.578)2 Kc = = = 1.

88(2.00 – x) = 1.3x +1.88x2 – 11.x 4.0 – 11.00 – x)(4. Chemical Equilibrium 959oC Equation: H2O (g) + CO (g)  H2 (g) + CO2 (g) I 2.00 .00 4.00 C -x -x +x +x E 2.00 0.6x – x2) x2 = 15.00 0.3x +15.0 02/26/17 16 .00 .00 – x) x2 = 1.88x2  0 = 0.00 – x)(4.x x x [H2][CO2] x2 Kc = = = 1.88(8.88 [H2O][CO] (2.00 .

88)(15. 0 = 0.0)]1/2 2(0.88) = 11 and 1.3)2 – 4(0.com/algebra-help.3 x + 15.88 x2 – 11.5 ! Which is RIGHT? 02/26/17 17 .freemathhelp.html -(-11.0 (ax2 + bx + c) Dust off the old Quadratic Formula: http://www.3) ± [(-11.

11 M can’t be right! 1. Chemical Equilibrium What is ‘x’? It is the concentration of H2 and CO2 at equilibrium! But…you can’t have more hydrogen gas than you have of reactants to begin with! Thus.5 M is the only sensible answer! 02/26/17 18 .

5 M Therefore: [H2O]eq = 0.8 There are no units in this case! What if you don’t remember the quadratic formula?? 02/26/17 19 .5 M Check: Kc = (1.5 M [CO]eq = 2. Chemical Equilibrium x = 1.5M)(2.5 M [H2]eq = [CO2]eq = 1.5M)2/(0.5M) = 1.

Use Successiv Approximation 02/26/17 20 .

00 Change (M) .67 x 10-7 A 0.50 x 10-1 – 2x) 2x x 02/26/17 21 .50 x 10-1 0.500-L vessel initially contains 1.00 0.25 x 10-1 mol of H2S.Class Exercise 14.5: Consider the following reaction for the decomposition of hydrogen sulfide: 800o C 2 H2S  2 H2 (g) + S2 (g) KC = 1.2x + 2x +x Equilibrium (M) (2. Equation: 2 H2S (g)  2 H2 (g) + S2 (g) Initial (M) 2. Find the equilibrium concentrations of H2 and S2.

Kc = [H2]2[S2] (2x)2x = H2S (2.67 x 10-7 (2.25 x 10-2) (1. Then: 4x3 4x3 = ~ 1.67 x 10-7) = 4x3 = 1.67 x 10-7 (2.50 x 10-1 – 2x)2 Assume x is NEGLIGIBLE compared to 2.50 x 10-1)2 6.61 x 10-9 x = 1.50 x 10-1 M.50 x 10-1 – 2x)2 4x3 = = 1.38 x 10-3 M 02/26/17 22 .25 x 10-2 (6.04 x 10-8 x3 = 2.

67 x 10-7 4.38 x 10-3 M? Plug it back in to check: 4x 3 4x 3 = (2.74 x 10-4 There appears to be a mistake in these calculations! Please check carefully and see if you can see where it is! 02/26/17 23 .50 x 10-1) .38 x 10-3)]2 4x3 = 1.2(1. Is x NEGLIGIBLE compared to 1.07 x 10-11 >>>>> x = 2.95 x 10-4 x3 = 2.50 x 10 – 2x) -1 2 [(2.

Complex example of Successive Approximation 02/26/17 24 .

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Do NOT Panic! This is NOT a typical Problem! It is a Worst Case Scenario!!! Any Exam Problem will be MUCH Shorter!! 02/26/17 30 .

212 02/26/17 [N2O4] 31 .020 00 M and [NO2]I = 0.030 96 [NO2]2 KC = = (0.000 00 C (M) -0. [N2O4]eq = 0. Class Exercise 14.030 96)2/(0. (a) What is [NO2]eq? (b) What is the value for Kc? Equation: N2O4 (g)  2 NO2 (g) I (M) 2.030 96 E (M) 4.015 48 +0.5: In an experiment starting with [N2O4]I = 0.004 52 M.000 x 10-2 0.000 00 M.52 x 10-3 0.004 52) = 0.

the closer to completion the rxn is! N2 (g) + O2 (g)  2 NO (g) KC = 1 x 10-30 2 NH3 (g)  N2 (g) + 3 H2 (g) KC = 9.33 x 1034 02/26/17 32 .5 H2 (g) + Cl2 (g)  2 HCl (g) KC = 1. What does the value of Kc MEAN? The larger KC is.