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Characteristics of Chemical Equilibrium
Many reactions fail to go to completion. [Reactants] stop decreasing, and [Products] stop increasing. The reaction reaches equilibrium. If there are more: products than reactants = product favored. reactants than products = reactant favored.
Equilibrium is Dynamic
Reactants convert to products aA+bB cC+dD BUT, products can also react to make reactants. Equilibrium occurs when [A], [B], [C] and [D] stop changing - a dynamic equilibrium:
• Species do not stop forming OR being destroyed. • Rate of formation = rate of removal. • Concentrations are constant.
Equilibrium is Independent of Direction
N2(g) + 3 H2(g)
Start with: 1 mol N2 + 3 mol H2
or with: 2 mol NH3
They will form identical equilibrium mixtures
Equilibrium & Catalysts Catalysts do not affect equilibrium concentrations. Catalysts: • speed up the forward reaction… • …but also speed up the reverse reaction. . • decrease the time needed to reach equilibrium.
The Equilibrium Constant 2-butene isomerization: At equilibrium: rateforward = ratereverse .
47 700 1.65 600 1. Kc: kforward Kc = = kreverse [trans] = 1.36 .The Equilibrium Constant The isomerization is elementary.65 (at 500 K) [cis] “c” concentration based Equilibrium constants are temperature dependent: T (K) Kc 500 1. so: kforward[cis] = kreverse[trans] or [trans] kforward = [cis] kreverse This ratio is named the equilibrium constant.
The Equilibrium Constant For a general reaction: aA+bB cC+dD Products raised to stoichiometric powers… kforward Kc = = kreverse [C]c [D]d [A]a [B]b …divided by reactants raised to their stoichiometric powers .
The Equilibrium Constant Examples N2(g) + O2(g) 2 NO(g) [NO]2 Kc = [N ] [O ] 2 2 1 8 S8(s) + O2(g) SO2(g) [SO2] Kc = [O ] 2 S8 is ignored. All pure solids are omitted from Kc. .
• This constant factor is “absorbed” into Kc. . wt S8 8 g/L g / mol • d and mol. wt. so [S8] is constant. density • pure solid concentration = mol. wt • [S8] = dS / mol. Pure liquids are omitted for the same reason.Equilibria Involving Pure Liquids & Solids [Solid] is constant throughout a reaction. are constants.
Equilibria in Dilute Solutions Water is omitted from Kc in dilute solution reactions: • It is in large excess (pure water = 55. [H2O] ≈ constant. NH3(aq) + H2O(ℓ) NH4+(aq) + OH-(aq) [NH4+][OH-] Kc = [NH ] = 1.5 M). • Even if consumed or produced.8 x 10-5 3 (at 25 C) (Units are customarily omitted from Kc) . • The constant factor is incorporated into Kc.
solution) [H2O]2 [SiH4][O2]2 Na2SO4(aq) + 2 H2O(ℓ) [Na2SO4] [H2SO4][NaOH]2 .The Equilibrium Constant What is the equilibrium constant for: SiH4(g) + 2 O2(g) SiO2(s) + 2 H2O(g) ? Omit SiO2 (a solid) Include H2O (a gas) Write down Kc for: 2 NaOH(aq) + H2SO4(aq) Omit H2O (aq.
• Multiply an equation by a factor… • … Raise Kc to the power of that factor.Kc for Related Reactions N2(g) + 3 H2(g) 2 NH3(g) [NH3]2 Kc = [N2][H2]3 …change Kc [NH3] Kc = ½[H ]3 2 [N2] 2 Change the stoichiometry… ½ N2(g) + 3 2 H2(g) ½(original reaction) NH3(g) This new Kc is the square root of the original Kc. .
Kc for Related Reactions N2(g) + 3 H2(g) 2 NH3(g) [NH3]2 Kc = [N2][H2]3 Reverse a reaction… 2 NH3(g) … Invert Kc: N2(g) + 3 H2(g) [N2][H2]3 Kc = [NH3]2 .
Kc for a Combined Reaction If a reaction can be written as a series of steps: step 1 N2(g) + O2(g) 2NO(g) 2 NO2(g) 2 NO2(g) [NO]2 Kc = [N2][O2] [NO2]2 Kc = [NO]2[O2] [NO2]2 Kc = [N2][O2]2 step 2 2 NO(g) + O2(g) overall N2(g) + 2 O2(g) The overall Kc is the product of the steps: [NO2]2 [NO]2 [NO2]2 Kc(step1) x Kc(step2) = = 2[O ] [N2][O2] [NO] 2 [N2][O2]2 .
so another K is used… . P is proportional to molar conc.Equilibrium Constants in Terms of P In a constant-V reaction. partial pressures change as concentrations change.: Ideal gas: and for gas A: PV = nRT PAV = nART nA RT = [A]RT PA= V P is easily measured. At constant T.
Equilibrium Constants in Terms of P For a gas-phase reaction: a A(g) + b B(g) c C(g) + d D(g) PCc PDd Kp = PAa PBb “p” pressure based In general: Kp = Kc(RT)Δngas with Δngas = ngaseous products − ngaseous reactants = (c + d) – (a + b) .
7 x 102 mol2 L-2 atm-2 Kp = 9. .8 x 105 @ 25 C.8 x 105 0.7 x 102 atm-2 mol and L units are assumed to cancel (units omitted from Kc).Equilibrium Constants in Terms of P Calculate Kp from Kc for: 2 NH3(g) N2(g) + 3 H2(g) Kp = Kc(RT)Δngas T = 25 + 273 = 298 K Δngas = 2 – (3 + 1) = −2 Kp = 5. Use R in L/mol units. [ ] has mol/L units.0821 L atm Kc = 5. -2 mol-1 K-1(298 K) = 9.
0 M.0 M & [B] = 4.0) .0 Kc = 2 = 1.0 (2. What is Kc? [B] kforward Kc = = [A]2 kreverse 4. Example Consider: 2 A (aq) B (aq) At equilibrium [A] = 2.Determining Equilibrium Constants If all the equilibrium concentrations are known it’s easy to calculate Kc for a reaction….
Determining Equilibrium Constants Determine Kc for these three equilibrium mixtures of 2-butene: [trans] (# of ) Kc = [cis] = (# of ) (45 ) =9 a) Kc = (5 ) c) Kc = (5 ) = ¹⁄9 (45 ) (25 ) b) Kc = =1 (25 ) .
Determine Kc.0100 mol/L and [I2]initial = 0.Determining Equilibrium Constants … In other cases stoichiometry is used to find some concentrations.00800 mol/L. H2(g) + I2(g) 2 HI(g) . Example H2(g) and I2(g) were added to a heated container. At equilibrium [I2] = 0.00560 mol/L. [H2]initial = 0.
Determining Equilibrium Constants Write a balanced equation.x 2x .01000 .x 0.00800 2 HI(g) 0 Let HI made = 2x Use stoichiometry to predict changes: [ ]change -x -x 2x 1H2 ≡ 2HI so H2 lost = x 1I2 ≡ 2HI so I2 lost = x Add [ ]initial and [ ]change to get [ ]equilib [ ]equilib 0. fill in [ ]initial: H2(g) + [ ]initial 0.00800 .01000 I2(g) 0.
x x = 0.x 2x Since [I2] = 0.01000 .00240) = 0.(0.00800 .00800 .00760)(0.00240 M [H2]equilib = 0.(0.01000 .00560 = 0.541 [H2][I2] (0.00760 M [I2]equilib = 0.00240) = 0.00240) = 0.00560 M at equilibrium 0.00480)2 Kc = = = 0.00560) .Determining Equilibrium Constants [ ]equilib H2(g) + 0.x I2(g) 2 HI(g) 0.00560 M [HI]equilib = 2(0.00480 M [HI]2 (0.00800 .
• usually written as “no reaction” or NR. . • assume reaction goes to completion. • use equilibrium methods discussed here. • very little product forms. Kc ≈ 1 Reactants & products present at equilibrium. • very little reactant remains. Kc << 1 Reaction is strongly reactant favored. • often written as a forward reaction only.Meaning of the Equilibrium Constant When: Kc >> 1 Reaction is strongly product favored.
Q can predict the direction of a reaction: For the reaction: aA + bB [C]c [D]d Q = [A]a [B]b cC + dD Q looks identical to Kc. (Kc = Q whenever a system is at equilibrium) .Predicting the Direction of a Reaction The reaction quotient. BUT… the concentrations are not equilibrium values.
Q must increase to reach equilibrium. • move back.Predicting the Direction of a Reaction [Products] Q = [Reactants] Changes as a reaction moves to equilibrium [Products]equilib Kc= [Reactants] equilib Constant! (If T is constant) If Q < Kc. Q must decrease to reach equilibrium. If Q > Kc. • make more product (and less reactant). . • make less product (and more reactant). • move forward.
Predicting the Direction of a Reaction .
5 (0. . Q must increase to reach equilibrium.250)2 Q = [SO ]2[O ] = 2(0. [ SO3]2 (0. O2 (0.100 M) and SO3 (0.100) = 86.085 M).250 M) are mixed in a reactor at 1000 K. • Need more product (less reactant). • Forward direction.085) 2 2 Q < Kc.Predicting the Direction of a Reaction 2 SO2(g) + O2(g) 2 SO3(g) Kc = 245 at 1000 K Predict the direction of the reaction if SO2 (0.
Calculating Equilibrium Concentrations If Kc is known. [ ]equilib can be calculated.0500 mol of HI is placed in an empty 1. K.00 L flask at 600. . Problem 2 HI(g) H2(g) + I2(g) 0. What will be [HI]. [H2] and [I2] at equilibrium? Kc = 76 at 600. K.
0500 – 2x)2 Kc = = [H2][I2] (x)(x) Since Kc = 76 76 x2 = (0.Calculating Equilibrium Concentrations H2(g) [ ]initial [ ]change [ ]equilib 0 1H2 ≡ 2HI + I2(g) 0 1I2 ≡ 2HI 2 HI(g) 0.0500 – 2x [HI]2 (0.0500 – 2x)2 .0500 Amount lost Change on reaching equilibrium: +x +x +x +x -2x 0.
718 x = (0.0500 – 2x) 10.718 x = 0.718 x = -0.0500 x = 4.Calculating Equilibrium Concentrations 76 x2 = (0.0500 – 2x)2 Take the square root of both sides: 8. .0500 x = -7.67 x 10-3 or or 6.44 x 10-3 Ignore the negative root (x cannot be negative).
00467 M [I2]equilib = x = 0.0407 M)2 Kc = = = 76. [H2][I2] (0.00467 M) .0407 M It’s a good idea to check your work: Matches Kc given in the problem [HI]2 (0.Calculating Equilibrium Concentrations So: [H2]equilib = x = 0.0500 – 2x = 0.00467 M [HI]equilib = 0.00467 M)(0.
500 [ ]Initial [ ]change [ ]equilib 0.100 . What are [A].100 -x (0.1000 – x) A quadratic equation .500 x – 0.1000 – x) [A] x2 + 2.Calculating Equilibrium Concentrations Enough A is added to an empty container so that [A]initial = 0.500 = (0.2500 = 0 x2 2.x) 0 x x 0 x x (x)(x) [B][C] Kc = = (0.1000 M. [B] and [C] at equilibrium? A(g) B(g) + C(g) Kc = 2.
Calculating Equilibrium Concentrations ax2 + bx + c = 0 has two roots (solutions): Here: 1x2 + 2.2500 = 0 a b c x= −2.500 (2.500 x – 0.0963 M .500)2 − (4)(1)(−0.596 M x = -b b2 .250) 2(1) or -2.4ac 2a x = +0.
093) Check: = = 2.1000 .5 = Kc [A] 0.0037 M [ B ] = x = 0.x = 0.Calculating Equilibrium Concentrations Ignore the negative root (negative concentration!) Then x = 0.0963 M.0963 M [ C ] = x = 0. and: [ A ] = 0.037 .093)(0. [B][C] (0.0963 M Most of the A is converted to products.
the system will react to reach a new equilibrium in a way that partially counteracts the change” • A system at equilibrium resists change. • If “pushed”.Le Chatelier’s Principle “If a system is at equilibrium and the conditions are changed so that it is no longer at equilibrium. it “pushes back” .
• the reaction shifts backward. • more reactant is created. • the reaction shifts forward. . Remove A (or B) the system adjusts to add more. • more product is created.Changing Concentrations aA + b B cC + dD Add A (or B) and the system adjusts to remove it.
Changing Concentrations .
Consider: N2O4(g) 2 NO2(g) If V doubles. goes to 5 moles in 2 L. [ NO2 ]2 Kc=Q= [ N2O4] At equilibrium (½[ NO2 ])2 ¼[ NO2 ]2 ½[ NO2 ]2 Q= = = = ½Kc ½[ N2O4] ½[ N2O4] [ N2O4] After V change. Equilibrium position may change.Changing V or P in Gaseous Equilibria K does not change if P or V change. all concentrations divide by 2: • 5 moles of NO2 in 1 L. • [NO2] = 5 M becomes [NO2] = 2.5 M. Equilibrium shifts towards products . Q < Kc.
P doubled. convert 2 molecules into 1. • Shifting toward products.Changing V or P in Gaseous Equilibria Consistent with Le Chatelier N2O4(g) 2 NO2(g) V doubled = lower concentration. • Shifting toward reactants. Minimize change by: • Making more molecules (increase concentration). convert 1 molecule into 2. Minimize the change by: • Removing molecules (decrease P). .
the system cannot adjust (there are 2 gas molecules on each side).Changing V or P in Gaseous Equilibria P and V changes have no effect if Δngas = 0: H2(g) + I2(g) 2 HI(g) If V is doubled. [HI]2 Kc=Q= [H2][I2] At equilibrium (½[HI])2 ¼[HI]2 [HI]2 Q = ½[H ]½[I ] = = = Kc ¼[H2][I2] [H2][I2] 2 2 After V change. Q = Kc still at equilibrium! .
nor do nreactants or nproducts… • … [reactant] and [product] do not change. nA RT = [A]RT PA= V . • Total P increases • V does not change.Changing V or P in Gaseous Equilibria Adding an inert gas to change P has no effect.
Changing V by Adding Solvent Kc is not changed by solvent addition or removal. H3O+(aq) + SO42-(aq) HSO4-(aq) + H2O(ℓ) [H3O+][SO42-] = 0.012 Kc = [HSO4-] (at 25 C) If the volume is doubled: • The concentration of every species halves • Q = ½ ½ Kc = ½Kc ½ • The equilibrium adjusts (moving toward products) . but equilibrium position may change.
Changing Temperature A change in T changes Kc. • Kc may increase or decrease if T is increased.5 x 10-31 6.5 kJ Kc increases as T increases. Explained by LeChatelier… .7 x 10-10 1. N2(g) + O2(g) T (K) 298 900 2300 Kc 4.7 x 10-3 2 NO(g) ΔH = 180.
releasing heat. • Equilibrium shifts in reverse. T reduced? Add heat. • Reverse reaction is exothermic. removing heat.5 kJ T increased? Minimize by removing heat. . • Equilibrium shifts forward.Changing Temperature N2(g) + O2(g) 2 NO(g) ΔH = 180. • Forward reaction is endothermic.
• Are more product favored at higher T. . • Are less product favored at higher T.Changing Temperature Exothermic reactions: • Kc decreases as T increases. Endothermic reactions: • Kc increases as T increases.
The Haber-Bosch Process Production of NH3 for fertilizer from atmospheric N2 N2(g) + 3 H2(g) 2 NH3(g) Process developed by Fritz Haber (chemist) and Carl Bosch (engineer). Perfected in 1914. Germany could not import guano from S. America and needed to make explosives… .
NH3 is continually liquefied and removed. and must be heated.2 kJ It is: • Exothermic = product favored at low-T. . • Uses a catalyst to speed the reaction. • Carried out at high-P (200 atm). but… • … very slow at room-T. Run at 450 C.The Haber-Bosch Process N2(g) + 3 H2(g) 2 NH3(g) ΔH = -92. to favor product.
The Haber-Bosch Process .