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Section 06 General Concepts of Chemical Equilibrium

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General Concepts: Chemical Equilibrium Chemical Reactions: The Rate Concept aA + bB cC + dD Rate f = k f [A] a [B] b Rate r = k r [C] c [D] d Rate f = Rate r k f [A] a [B] b = k r [C] c [D] d Molar Equilibrium Constant K K = k f / k r =([C] c [D] d )/([A] a [B] b ) Not Generally Valid, because reaction rates depend on mechanisms

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Fig Progress of a chemical reaction. The rate of the forward reaction diminishes with time, while that of the backward reaction increases, until they are equal. A large K means the reaction lies far to the right at equilibrium. The rate of the forward reaction diminishes with time, while that of the backward reaction increases, until they are equal. A large K means the reaction lies far to the right at equilibrium. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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Equilibrium constants may be written for dissociations, associations, reactions, or distributions. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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General Concepts: Chemical Equilibrium Gibbs Free Energy & Equilibrium Constant G = H – TS but H = E + PV –G = Gibbs Free Energy H = Enthalpy –T = TemperatureS = Entropy –E = Internal Energy P = Pressure V = Volume G = E + PV – TS but E = q – w G = q – w + PV - TS Derivative dG = dq - dw + PdV + VdP – TdS – SdT

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General Concepts: Chemical Equilibrium dG = dq - dw + PdV + VdP – TdS – SdT Let’s Simplify by imposing some conditions on the reaction. Constant Temperature: dT = 0 SdT = 0 Reversible Reaction: dq = TdS Expansion work only: dw = PdV Then all terms except one cancel dG = VdP 1mole of an ideal gas V = RT/P dG = RTdP/P

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General Concepts: Chemical Equilibrium Now lets integrate: dG = RTdP/P Result: G 2 -G 1 = RTln(P 2 /P 1 ) make state 1 = standard state G – G o = RTln(P/P o )but P o = 1 atm Activity is defined: a = P/P o G = G o + RTln(a)

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General Concepts: Chemical Equilibrium General Expressions: rR + sS tT + uU G = tG T + uG U – rG R + sG S Each Free Energy Term Expressed in Terms of Activity tG T = tG T o + t RT ln a T uG U = uG U o + u RT ln a U rG R = rG R o + r RT ln a R sG S = sG S o + s RT ln a S G = G o + RT ln (a T t a U u /a R r a S s )

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General Concepts: Chemical Equilibrium G = G o + RT ln (a T t a U u /a R r a S s ) At Equilibrium: G = 0 Reaction quotient Q = (a T t a U u /a R r a S s ) = K o Where K o is the thermodynamic equilibrium constant 0 = G o + RT ln K o ln K o = - G o /RT K o = e (- G o /RT)

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Chemical Equilibrium Review of Principles Chemical reactions are never “complete” Chemical reactions proceed to a state where ratio of products to reactants is constant NH 3 + HOH NH OH - [NH 4 + ][OH - ]/[NH 3 ][HOH] = K b o If K b << 1 (little ionization) H 2 SO 4 + HOH H 3 O + + HSO 4 - [H 3 O + ][HSO 4 - ] / [H 2 SO 4 ][HOH] = K a If K a >> 1 (mostly ionized)

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Chemical Equilibrium Equilibrium –is not reached instantaneously –can be approached from either direction –is a dynamic state –amounts of reactants/products can be changed by “mass action” –(adding/ deleting products/reactants) –HCO H + CO 2(g) + HOH –K e = [CO 2 ][HOH]/[HCO 3 - ][H + ]

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Chemical Equilibrium Equilibrium Constants 2 A + 3 B C + 4 D K e = [C][D] 4 /[A] 2 [B] 3 Concentrations [ ] : –molar for solutes –partial pressures (atm) for gases –[1.0] for pure liquid, solid, or solvent

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Chemical Equilibrium Important Equilibria in Analytical Chemistry Solubility: AgCl(s) Ag + + Cl - Ag 3 AsO 4 (s) 3 Ag + + AsO 4 3- BaSO 4 (s) Ba 2+ + SO 4 2- K sp (AgCl) = [Ag + ][Cl - ] = 1.0 x K sp (Ag 3 AsO 4 ) = [Ag + ] 3 [AsO 4 3- ] = 1.0 x K sp (BaSO 4 ) = [Ba 2+ ][SO 4 2- ] = 1.0 x

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Chemical Equilibrium Important Equilibria in Analytical Chemistry Autoprotolysis: HOH + HOH H 3 O + + OH - K e = [H 3 O + ][OH - ]/[HOH] 2 K e [HOH] 2 = K w = [H 3 O + ][OH - ] = 1.0 x o C In pure 25 o C [H 3 O + ] = [OH - ] = Acid Dissociation: H 2 CO 3 + HOH H 3 O + + HCO 3 - K a = [H 3 O + ][HCO 3 - ]/[H 2 CO 3 ] = 4.3 x 10 -7

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Chemical Equilibrium Important Equilibria in Analytical Chemistry H 2 CO 3 + HOH H 3 O + + HCO 3 - acid 1 base 1 Dissociation of Conjugate Base 1 : HCO HOH H 3 O + + CO 3 2- K a (HCO 3 - ) = [H 3 O + ][CO 3 2- ]/[HCO 3 - ] = 4.8 x Hydrolysis of Conjugate Base 1 : HCO HOH H 2 CO 3 + OH - K b (HCO 3 - ) = K w /K a (H 2 CO 3 ) = /4.3x K b (HCO 3 - ) = 2.3 x 10 -8

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Chemical Equilibrium Important Equilibria in Analytical Chemistry Base Dissociation: NH 3 + HOH NH OH - K b (NH 3 ) = [NH 4 + ][OH - ]/[NH 3 ] = 1.75 x Hydrolysis of Salts: NH 4 Cl(s) NH Cl - NH HOH NH 3 + H 3 O + K a (NH 4 + ) = K w /K b (NH 3 ) = /1.75 x K a (NH 4 + ) = 5.7 x

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Chemical Equilibrium Some Useful Calculations Common Ion Effects on Solubility: What is the solubility of BaF 2 in pure water? What is the solubility of BaF 2 in 0.1 M NaF?

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Chemical Equilibrium Some Useful Calculations pH of Weak Acid or Base Solutions:

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Chemical Equilibrium Electrolyte Effects Electrolytes: Substances producing ions in solutions Can electrolytes affect chemical equilibria? (A) “Common Ion Effect” Yes –Decreases solubility of BaF 2 with NaF –F - is the “common ion” (B) No common ion: “inert electrolyte effect”or “diverse ion effect” –Add Na 2 SO 4 to saturated solution of AgCl –Increases solubility of AgCl Why???

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Activity and Activity Coefficients Activity of an ion, a i = C i ƒ i C i = concentration of the ion ƒ i = activity coefficient C i < M )= 1 Ionic Strength, = ½ C i Z i 2 Z i = charge on each individual ion.

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Activity and Activity Coefficients Calculation of Activity Coefficients Debye-Huckel Equation: -log ƒ i = 0.51Z i 2 ½ i ½ i = ion size parameter in angstrom (Å) 1 Å = 100 picometers (pm, meters) Limitations: singly charged ions = 3 Å -log ƒ i = 0.51Z i 2 ½ ½

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Chemical Equilibria Electrolyte Effects Diverse ion (Inert) electrolyte effect –For < 0.1 M, electrolyte effect depends on only, NOT on the type of electrolyte Solute activities: a x = activity of solute X a x = [X] x x = activity coefficient for X As x 1, a x [X]

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Chemical Equilibria Electrolyte Effects Diverse Ion (Inert Electrolyte) Effect: Add Na 2 SO 4 to saturated solution of AgCl K sp o = a Ag +. a Cl - = 1.75 x At high concentration of diverse (inert) electrolyte: higher ionic strength, a Ag + < [Ag + ] ; a Cl - < [Cl - ] a Ag +. a Cl - < [Ag + ] [Cl - ] K sp o < [Ag + ] [Cl - ] ; K sp o < [Ag + ] = solubility Solubility = [Ag + ] > K sp o

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Chemical Equilibria Electrolyte Effects “Diverse ion (Inert) electrolyte effect” Is dependent on parameter called “ionic strength ( ” = (1/2) {[A]Z A 2 + [B]Z B 2 + … + [Y]Z y 2 } 0.1 M Na 2 SO 4 ; [Na + ] = 0.2M [SO 4 ] = 0.1M = (1/2) {[A]Z A 2 + [B]Z B 2 } = (1/2) {[0.2](1+) 2 + [0.1](2-) 2 } = 0.3M

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Chemical Equilibria Electrolyte Effects Solute activities: When is not zero, a x = [X] x Equilibrium effects: mM + xX zZ K o =(a z ) z /(a m ) m (a x ) x K o =( [Z] Z ) z /( [M] M ) m ( [X] x ) x K o ={( [Z] ) z /( [M] ) m ( [X] ) x }{ Z z / M m x x } K o = K { Z z / M m x x } K = K o { M m x x / Z z }

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The Diverse Ion Effect The Thermodynamic Equilibrium Constant and Activity Coefficients –thermodynamic equilibrium constant, K o –case extrapolated to infinite dilution –At infinite dilution, activity coefficient, ƒ = 1 Dissociation AB A + + B - K o = a A a B /a AB = [A + ] ƒ A. [B - ] ƒ B / [AB] ƒ AB K o = K (ƒ A. ƒ B / ƒ AB ) K = K o (ƒ AB / ƒ A. ƒ B )

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Chemical Equilibria Electrolyte Effects Calculation of Activity Coefficients Debye-Huckel Equation: -log ƒ x = 0.51Z i 2 ½ i ½ Where x = effective diameter of hydrated ion, X (in angstrom units, cm), Å IonH3O+H3O+ Li + F-F- Ca 2+ Al 3+ Sn 4+ x,, Å ƒ 0.05 M

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Chemical Equilibrium Electrolyte Effects Equilibrium calculations using activities: Solubility of PbI 2 in 0.1M KNO 3 2 (ignore Pb 2+,I - ) ƒ Pb = 0.35 ƒ I = 0.76 K sp o = (a Pb ) 1 (a I ) 2 = ([Pb 2+ ] Pb ) 1 ([I - ] I ) 2 K sp o = ([Pb 2+ ] [I - ] 2 )( Pb I 2 ) = K sp ( Pb I 2 ) K sp = K sp o / ( Pb I ) K sp = 7.1 x /((0.35)(0.76) 2 ) = 3.5 x (s)(2s) 2 = K sp s = (Ksp/4) 1/3 s =2.1 x M Note: If s = (K sp o /4) 1/3 thens =1.2 x M Solubility calculation difference approx. –43%

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Multiple Chemical Equilibria Compositional Calculations Setting up the problem: Write balanced equations for all equilibria Write K e expressions and find values Write mass and charge balance equations Write expression for sought for substance Determine in No. independent equations (N) at least equals No. of unknowns (U) –(if N < U can approximations reduce U?) Make approximations to simplify math Solve set of equations for all unknowns Check validity of assumptions –(re-solve with second approximation if needed)

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Multiple Chemical Equilibria Dissolve NaHCO 3 in water: –NaHCO 3 Na + + HCO 3 - HCO HOH H 2 CO 3 + OH - K e = Kb = Kw/K a1 HCO HOH H 3 O + + CO 3 2- K e = K a2 HOH + HOH H 3 O + + OH - K e = K w 5 chemical species affected by 3 equilibria Equilibrium constants do NOT change with chemical additions/ deletions –Add Ba 2+ : Ba 2+ + CO 3 2- BaCO 3(s) K e = K sp –(Now there are 6 species affected by 4 equilibria) Note: For Polyprotic Acids (H N A): K (step) = K a1, K a2,-- K aN H 2 A + HOH H 3 O + + HA - K e = K a1 HA - + HOH H 3 O + + A 2- K e = K a2

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Multiple Chemical Equilibria Compositional Calculations What are concentrations of individual species? For N species, M equilibria Need, N independent algebraic expressions: Equilibrium expressions (M < N) Mass balance statements Charge Balance statements

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Multiple Chemical Equilibria Compositional Calculations Mass Balance Equations: Relate equilibrium concentrations of species –Stoichiometric relationships –How the solution was prepared –What kinds of equilibria exist E.g. 0.1 M HNO 2 (C HA = 0.1 M) HNO 2 + HOH H 3 O + + NO 2 - K e = K a C HA (x)(x) HOH + HOH H 3 O + + OH - K e = K w (w)(w) C HA = [HNO 2 ] + [NO 2 - ]all forms of “HNO 2 ” [H 3 O + ] = [OH - ] + [NO 2 - ] = w + x [H 3 O + ] from 2 sources

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Multiple Chemical Equilibria Compositional Calculations Charge Balance Equations: In any electrolyte solution, amt. of positive charge = amt. of negative charge solution charge for each species = [conc.][charge/ion] E.g. for solution MgCO 3 MgCO 3 _ Mg 2+ + CO 3 2- leads to equilibria: CO HOH HCO OH - HCO HOH H 2 CO 3 + OH - Charge Balance: 2[Mg 2+ ] + [H 3 O + ] = 2[CO 3 2- ] + [HCO 3 - ] + [OH - ]

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Systematic Approach to Equilibrium Calculations How to Solve Any Equilibrium Problem 1. Write balanced chemical reactions 2. Write equilibrium constant expressions 3. Write all mass balance expressions 4. Write the charge balance expression 5. Equations >= Chemical Species sol possible 6. Make assumptions where possible 7. Calculate answer 8. Check validity of assumptions

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Multiple Chemical Equilibria Example Problem #1 What is pH of Mg(OH) 2 solution ? (assume a x = [X]) Equilibria: Mg(OH) 2(s) Mg OH - K sp = [Mg 2+ ][OH - ] = 1.8 x HOH + HOH H 3 O + + OH - K e = K w = 1.0 x Mass Balance: [OH - ] = [H 3 O + ] + 2 [Mg 2+ ] Charge Balance: [OH - ] = [H 3 O + ] + 2 [Mg 2+ ] Expression for unknown : [H 3 O + ] = K w / [OH - ]

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Multiple Chemical Equilibria Example Problem #1 What is pH of Mg(OH) 2 solution ? (assume a x = [X]) Expression for unknown : [H 3 O + ] = K w / [OH - ] Solution: Assume [H 3 O + ] << 2 [Mg 2+ ] ; [OH - ] = 2 [Mg 2+ ] Substitute into K sp, K sp = ([OH - ] /2)([OH - ]) 2 [OH - ] 3 = 2 K sp ; [OH - ] = (2 K sp ) 1/3 = 3.3 x M [H 3 O + ] = K w /(3.3 x ) = 3.0 x M pH = -log [H 3 O + ] = (2 sig figs) Note: original approximation was OK! i.e. [H 3 O + ] << [OH - ] (3.0 x << 3.3 x ) Assumed [OH - ] = 2 [Mg 2+ ] ; [H 3 O + ] << 2 [Mg 2+ ] Assumed [H 3 O + ] << [OH - ] OK!

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Multiple Chemical Equilibria Example Problem #2 What is pH of 0.1 M Na 3 PO 4 solution? (C s = 0.1 M) Na 3 PO 4(s) 3Na + + PO 4 3- Equilibria: (1) PO HOH HPO OH - K w /K a3 = 2.38 x (2) HPO HOH H 2 PO OH - K w /K a2 = 1.6 x (3) H 2 PO HOH H 3 PO 4 + OH - K w /K a1 = 1.4 x (4) HOH + HOH H 3 O + + OH - K w = 1.0 x Mass Balance Equations: (5) C s = [PO 4 3- ] + [HPO 4 2- ] + [H 2 PO 4 - ] + [H 3 PO 4 ] (6) [OH - ] = [H 3 O + ] + [HPO 4 2- ] + [H 2 PO 4 - ] + [H 3 PO 4 ] (*) K a1 = 7.1 x K a2 = 6.3 x K a3 = 4.2 x

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Multiple Chemical Equilibria Example Problem #2 What is pH of 0.1 M Na 3 PO 4 solution? (C s = 0.1 M) Charge Balance: (7) [H 3 O + ] + [Na + ] = [OH - ] + [H 2 PO 4 - ] + 2 [HPO 4 2- ] + 3 [PO 4 3- ] Note: [Na + ] = 3 C s Is problem solvable? 6 unknowns [H 3 O + ],[OH - ],[H 2 PO 4 - ],[HPO 4 2- ],[PO 4 3- ], [H 3 PO 4 ] 7 equations (see 1-7) Thus, the problem should be solvable.

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Multiple Chemical Equilibria Example Problem #2 (solution) What is pH of 0.1 M Na 3 PO 4 solution? (C s = 0.1 M) Assume [H 3 O + ] + [H 2 PO 4 - ] + [H 3 PO 4 ] << [HPO 4 2- ] Then from equation (6): [OH - ] = [HPO 4 2- ] = x Also Assume [HPO 4 2- ] + [H 2 PO 4 - ] + [H 3 PO 4 ] << [PO 4 3- ] Then from equation (5): [PO 4 3- ] = C s = 0.1 M equation (1): [HPO 4 2- ] [OH - ]/ [PO 4 3- ] = K w /K a3 = 2.38 x Thus x 2 /C s = 2.38 x x = [OH - ] = 4.9 x [H 3 O + ] = K w /[OH - ] = 2.0 x M pH = (2 sig fig) Note: Check assumptions

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Multiple Chemical Equilibria Example Problem #2 Check Assumptions:

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Excel Solver to solve the quadratic formula for Example 6.1. Solve 0.70x x – 0.30 = 0. First prepare a spreadsheet containing: 1.Cells containing the constants a, b, and c to be used in the formula, 0.70, 0.21, -0.30: (B3, B4, B5). 2.Cell for the variable, x, to be solved for: ($C$7). 3.Cell containing the formula 0.70x x – 0.30 (ES) (do not enter = 0): =B3*C7^2+B4*C7+B5 (continued next slide) Solve 0.70x x – 0.30 = 0. First prepare a spreadsheet containing: 1.Cells containing the constants a, b, and c to be used in the formula, 0.70, 0.21, -0.30: (B3, B4, B5). 2.Cell for the variable, x, to be solved for: ($C$7). 3.Cell containing the formula 0.70x x – 0.30 (ES) (do not enter = 0): =B3*C7^2+B4*C7+B5 (continued next slide) ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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Excel Solver to solve the quadratic formula for Example 6.1. Click on Solver to open the parameters dialogue box. Need to enter 3 parameters: 1.Set Target Cell: enter the cell containing the formula (E5). 2.Equal To: enter the value the equation is set to (0). 3.By Changing Cells: enter the cell containing the variable, x (C7). Then click Solve. The variable x will be changed by iteration until the equation equals zero. (continued next slide) Click on Solver to open the parameters dialogue box. Need to enter 3 parameters: 1.Set Target Cell: enter the cell containing the formula (E5). 2.Equal To: enter the value the equation is set to (0). 3.By Changing Cells: enter the cell containing the variable, x (C7). Then click Solve. The variable x will be changed by iteration until the equation equals zero. (continued next slide) ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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The solved quadratic formula. Click on Solve, and you receive a message that “Solver found a solution.” The answer is x = The formula after iteration is equal to –8E-08, essentially equal to zero. Click on Solve, and you receive a message that “Solver found a solution.” The answer is x = The formula after iteration is equal to –8E-08, essentially equal to zero. ©Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

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