Section 06

General Concepts of Chemical Equilibrium

General Concepts: Chemical Equilibrium

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

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.

Fig. 6.1. Progress of a chemical reaction.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Equilibrium constants may be written for dissociations, associations, reactions, or distributions.

Gary Christian, Analytical Chemistry,

6th Ed. (Wiley)

General Concepts: Chemical Equilibrium

Gibbs Free Energy & Equilibrium Constant G = H TS but H = E + PV
G = Gibbs Free Energy H = Enthalpy T = Temperature S = 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

General Concepts: Chemical Equilibrium

dG = dq - dw + PdV + VdP TdS SdT Lets 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

General Concepts: Chemical Equilibrium

Now lets integrate: dG = RTdP/P Result: G2-G1 = RTln(P2/P1) make state 1 = standard state G Go = RTln(P/Po) but Po = 1 atm Activity is defined: a = P/Po G = Go + RTln(a)

General Concepts: Chemical Equilibrium

General Expressions: rR + sS tT + uU DG = tGT + uGU rGR + sGS Each Free Energy Term Expressed in Terms of Activity tGT = tGTo + t RT ln aT uGU= uGUo + u RT ln aU rGR = rGRo + r RT ln aR sGS = sGSo + s RT ln aS DG = DGo + RT ln (aTt aUu/aRr aSs)

General Concepts: Chemical Equilibrium

DG = DGo + RT ln (aTt aUu/aRr aSs) At Equilibrium: DG = 0 Reaction quotient Q = (aTt aUu/aRr aSs) = Ko Where Ko is the thermodynamic equilibrium constant 0 = DGo + RT ln Ko ln Ko = - DGo/RT

Ko = e(- DGo/RT)

Chemical Equilibrium
Review of Principles Chemical reactions are never complete Chemical reactions proceed to a state where ratio of products to reactants is constant NH3 + HOH NH4+ + OH [NH4+][OH-]/[NH3][HOH] = Kbo If Kb << 1 (little ionization) H2SO4 + HOH H3O+ + HSO4 [H3O+][HSO4-] / [H2SO4][HOH] = Ka If Ka >> 1 (mostly ionized)

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) HCO3- + H+ CO2(g) + HOH Ke = [CO2][HOH]/[HCO3-][H+]

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

Chemical Equilibrium
Important Equilibria in Analytical Chemistry Solubility: AgCl(s) Ag+ + ClAg3AsO4(s) 3 Ag+ + AsO43BaSO4(s) Ba2+ + SO42Ksp(AgCl) = [Ag+][Cl-] = 1.0 x 10-10 Ksp(Ag3AsO4) = [Ag+]3[AsO43-] = 1.0 x 10-22 Ksp(BaSO4) = [Ba2+][SO42-] = 1.0 x 10-10

Chemical Equilibrium
Important Equilibria in Analytical Chemistry Autoprotolysis: HOH + HOH H3O+ + OHKe = [H3O+][OH-]/[HOH]2 Ke[HOH]2 = Kw = [H3O+][OH-] = 1.0 x 10-14 @ 25oC In pure water @ 25oC [H3O+] = [OH-] = 10-7 Acid Dissociation: H2CO3 + HOH H3O+ + HCO3Ka = [H3O+][HCO3-]/[H2CO3] = 4.3 x 10-7

Chemical Equilibrium
Important Equilibria in Analytical Chemistry H2CO3 + HOH H3O+ + HCO3acid1 base1 Dissociation of Conjugate Base1: HCO3- + HOH H3O+ + CO32Ka(HCO3-) = [H3O+][CO32-]/[HCO3-] = 4.8 x 10-11 Hydrolysis of Conjugate Base1: HCO3- + HOH H2CO3 + OHKb(HCO3-) = Kw/Ka(H2CO3) = 10-14/4.3x 10-7 Kb(HCO3-) = 2.3 x 10-8

Chemical Equilibrium
Important Equilibria in Analytical Chemistry Base Dissociation: NH3 + HOH NH4+ + OHKb(NH3) = [NH4+][OH-]/[NH3] = 1.75 x 10-5 Hydrolysis of Salts: NH4Cl(s) NH4+ + ClNH4+ + HOH NH3 + H3O+ Ka(NH4+) = Kw/Kb(NH3) = 10-14/1.75 x 10-5 Ka(NH4+) = 5.7 x 10-10

Chemical Equilibrium
Some Useful Calculations Common Ion Effects on Solubility: What is the solubility of BaF2 in pure water?

What is the solubility of BaF2 in 0.1 M NaF?

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

Chemical Equilibrium Electrolyte Effects

Electrolytes: Substances producing ions in solutions Can electrolytes affect chemical equilibria? (A) Common Ion Effect Yes
Decreases solubility of BaF2 with NaF F- is the common ion

(B) No common ion: inert electrolyte effector diverse ion effect

Add Na2SO4 to saturated solution of AgCl Increases solubility of AgCl Why???

Activity and Activity Coefficients

Activity of an ion, ai = Cii Ci = concentration of the ion i = activity coefficient ( @ Ci < 10-4M )= 1 Ionic Strength, m = SCiZi2 Zi = charge on each individual ion.

Activity and Activity Coefficients

Calculation of Activity Coefficients Debye-Huckel Equation: -log i = 0.51Zi2(m) / (1+0.33ai (m)) ai = ion size parameter in angstrom () 1 = 100 picometers (pm, 10-10 meters) Limitations: singly charged ions = 3 -log i = 0.51Zi2(m) / (1+ (m))

Chemical Equilibria Electrolyte Effects

Diverse ion (Inert) electrolyte effect
For m < 0.1 M, electrolyte effect depends on m only, NOT on the type of electrolyte

Solute activities:

ax = activity of solute X ax = [X]x

x = activity coefficient for X

As m 0, x 1,

ax [X]

Chemical Equilibria Electrolyte Effects

Diverse Ion (Inert Electrolyte) Effect: Add Na2SO4 to saturated solution of AgCl

Kspo = aAg+ . aCl- = 1.75 x 10-10

At high concentration of diverse (inert) electrolyte: higher ionic strength, m

aAg < [Ag ] ; aCl < [Cl ] aAg . aCl < [Ag ] [Cl ]
+

Kspo < [Ag+] [Cl-] ; Kspo < [Ag+] = solubility Solubility = [Ag+] > Kspo

Chemical Equilibria Electrolyte Effects Diverse ion (Inert) electrolyte effect Is dependent on parameter called ionic strength (m) m = (1/2) {[A]ZA2 + [B]ZB2 + + [Y]Zy2}
0.1 M Na2SO4 ; [Na+] = 0.2M [SO4] = 0.1M

m = (1/2) {[A]ZA2 + [B]ZB2} m = (1/2) {[0.2](1+)2 + [0.1](2-)2} = 0.3M

Chemical Equilibria Electrolyte Effects

Solute activities: When m is not zero, x = [X]x Equilibrium effects: mM + xX zZ

Ko =(az)z/(am)m(ax)x Ko =([Z]Z )z/([M]M )m([X]x )x Ko ={([Z])z/([M])m([X])x }{Z z/ M m x x}

Ko = K {Z z/ M m x x} K = Ko {M m x x / Z z}

The Diverse Ion Effect

The Thermodynamic Equilibrium Constant and Activity Coefficients
thermodynamic equilibrium constant, Ko case extrapolated to infinite dilution At infinite dilution, activity coefficient, = 1

Dissociation AB A+ + BKo = aA aB/aAB = [A+] A . [B-] B / [AB] AB Ko = K (A . B / AB) K = Ko (AB / A . B )

Chemical Equilibria Electrolyte Effects

Calculation of Activity Coefficients Debye-Huckel Equation: -log x = 0.51Zi2(m) / (1+0.33ai (m)) Where ax = effective diameter of hydrated ion, X (in angstrom units, 10-8cm), Ion H3O+ Li+ FCa2+ Al3+
a x ,, 9 6 .84 3.5 .81 6 .48 9 .24 x @ .86 0.05 M

Sn4+ 11 .1

Chemical Equilibrium Electrolyte Effects

Equilibrium calculations using activities: Solubility of PbI2 in 0.1M KNO3 m = 0.1 = {0.1(1+)2 + 0.1(1-)2}/2 (ignore Pb2+,I-) Pb = 0.35 I = 0.76 Kspo = (aPb)1(aI)2 = ([Pb2+]Pb )1([I-]I )2 Kspo = ([Pb2+] [I-]2)(Pb I2 ) = Ksp (Pb I2 ) Ksp = Kspo / (Pb I ) Ksp = 7.1 x 10-9 /((0.35)(0.76)2) = 3.5 x 10-8 (s)(2s)2 = Ksp s = (Ksp/4)1/3 s =2.1 x 10-3 M Note: If s = (Kspo/4)1/3 then s =1.2 x 10-3M Solubility calculation difference approx. 43%

Multiple Chemical Equilibria Compositional Calculations

Setting up the problem: Write balanced equations for all equilibria Write Ke 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)

Multiple Chemical Equilibria

Dissolve NaHCO3 in water:
NaHCO3 Na+ + HCO3HCO3- + HOH H2CO3 + OHKe = Kb = Kw/Ka1 HCO3- + HOH H3O+ + CO32Ke = Ka2 HOH + HOH H3O+ + OHKe = Kw 5 chemical species affected by 3 equilibria Equilibrium constants do NOT change with chemical additions/ deletions
Add Ba2+: Ba2+ + CO32- BaCO3(s) Ke = Ksp (Now there are 6 species affected by 4 equilibria)

Note: For Polyprotic Acids (HNA): K(step) = Ka1, Ka2,-- KaN H2A + HOH H3O+ + HAKe = Ka1 HA- + HOH H3O+ + A2Ke = Ka2

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

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 HNO2 (CHA = 0.1 M) HNO2 + HOH H3O+ + NO2- Ke = Ka CHA (x) (x) HOH + HOH H3O+ + OH- Ke = Kw (w) (w) CHA = [HNO2] + [NO2-] all forms of HNO2 [H3O+] = [OH-] + [NO2-] = w + x [H3O+] from 2 sources

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 MgCO3 MgCO3 _ Mg2+ + CO32- leads to equilibria: CO32- + HOH HCO3- + OHHCO3- + HOH H2CO3 + OHCharge Balance: 2[Mg2+] + [H3O+] = 2[CO32-] + [HCO3-] + [OH-]

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

Multiple Chemical Equilibria Example Problem #1

What is pH of Mg(OH)2 solution ? (assume ax= [X]) Equilibria:
Mg(OH)2(s) Mg2+ + 2 OH- Ksp = [Mg2+][OH-] = 1.8 x 10-11

HOH + HOH H3O+ + OH- Ke = Kw = 1.0 x 10-14 Mass Balance: [OH-] = [H3O+] + 2 [Mg2+] Charge Balance: [OH-] = [H3O+] + 2 [Mg2+] Expression for unknown : [H3O+] = Kw/ [OH-]

Multiple Chemical Equilibria Example Problem #1

What is pH of Mg(OH)2 solution ? (assume ax= [X]) Expression for unknown : [H3O+] = Kw/ [OH-] Solution: Assume [H3O+] << 2 [Mg2+] ; [OH-] = 2 [Mg2+] Substitute into Ksp, Ksp = ([OH-] /2)([OH-])2 [OH-]3 = 2 Ksp ; [OH-] = (2 Ksp)1/3 = 3.3 x 10-4 M [H3O+] = Kw/(3.3 x 10-4) = 3.0 x 10-11 M pH = -log [H3O+] = 10.52 (2 sig figs) Note: original approximation was OK! i.e. [H3O+] << [OH-] (3.0 x 10-11 << 3.3 x 10-4) Assumed [OH-] = 2 [Mg2+] ; [H3O+] << 2 [Mg2+] Assumed [H3O+] << [OH-] OK!

Multiple Chemical Equilibria Example Problem #2

What is pH of 0.1 M Na3PO4 solution? (Cs = 0.1 M) Na3PO4(s) 3Na+ + PO43 Equilibria:

(1) PO43- + HOH HPO42- + OH(2) HPO42- + HOH H2PO4- + OH(3) H2PO4- + HOH H3PO4 + OH(4) HOH + HOH H3O+ + OH-

Kw/Ka3 = 2.38 x 10-2 Kw/Ka2 = 1.6 x 10-9 Kw/Ka1 = 1.4 x 10-12 Kw = 1.0 x 10-14

Mass Balance Equations:

(5) Cs = [PO43-] + [HPO42-] + [H2PO4-] + [H3PO4] (6) [OH-] = [H3O+] + [HPO42-] + [H2PO4-] + [H3PO4]
(*) Ka1 = 7.1 x 10-3 Ka2 = 6.3 x 10-8 Ka3 = 4.2 x 10-13

Multiple Chemical Equilibria Example Problem #2

What is pH of 0.1 M Na3PO4 solution? (Cs = 0.1 M)

Charge Balance:
(7) [H3O+] + [Na+] = [OH-] + [H2PO4-] + 2 [HPO42-] + 3 [PO43-]
Note: [Na+] = 3 Cs

Is problem solvable? 6 unknowns [H3O+] ,[OH-],[H2PO4-],[HPO42-],[PO43-], [H3PO4] 7 equations (see 1-7) Thus, the problem should be solvable.

Multiple Chemical Equilibria Example Problem #2 (solution)

What is pH of 0.1 M Na3PO4 solution? (Cs = 0.1 M) Assume [H3O+] + [H2PO4-] + [H3PO4] << [HPO42-] Then from equation (6): [OH-] = [HPO42-] = x Also Assume [HPO42-] + [H2PO4-] + [H3PO4] << [PO43-] Then from equation (5): [PO43-] = Cs = 0.1 M equation (1): [HPO42-] [OH-]/ [PO43-] = Kw/Ka3 = 2.38 x 10-2 Thus x2/Cs = 2.38 x 10-2 x = [OH-] = 4.9 x 10-2 [H3O+] = Kw/[OH-] = 2.0 x 10-13M

pH = 12.69 (2 sig fig)

Note: Check assumptions

Multiple Chemical Equilibria Example Problem #2

Check Assumptions:

Solve 0.70x2 + 0.21x 0.30 = 0. First prepare a spreadsheet containing: 1. 2. 3. Cells containing the constants a, b, and c to be used in the formula, 0.70, 0.21, -0.30: (B3, B4, B5). Cell for the variable, x, to be solved for: ($C$7). Cell containing the formula 0.70x2 +0.21x 0.30 (ES) (do not enter = 0): =B3*C7^2+B4*C7+B5 (continued next slide)

Excel Solver to solve the quadratic formula for Example 6.1.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Click on Solver to open the parameters dialogue box. Need to enter 3 parameters: 1. 2. 3. Set Target Cell: enter the cell containing the formula (E5). Equal To: enter the value the equation is set to (0). By Changing Cells: enter the cell containing the variable, x (C7). (continued next slide)

Then click Solve. The variable x will be changed by iteration until the equation equals zero.

Excel Solver to solve the quadratic formula for Example 6.1.

Gary Christian, Analytical Chemistry, 6th Ed. (Wiley)

Click on Solve, and you receive a message that Solver found a solution.

The answer is x = 0.10565.

The formula after iteration is equal to 8E-08, essentially equal to zero.

The solved quadratic formula.

Gary Christian, Analytical Chemistry,

6th Ed. (Wiley)