Ionic Equilibria

Compiled by Dr. L. Coo

Acids and Bases

1. Arrhenius Theory
(Svante Arrhenius,1884)

Acid = a substance that contains hydrogen and produces H+ in aqueous soln. Base = a substance that contains the OH (hydroxyl) group and produces hydroxide ions (OH-) in aq. soln.
(explains rxns bet protic acids and metal hydroxides)

Neutralization rxn: H+(aq) + OH-(aq)

H2O(l)

2. Bronsted-Lowry Theory (J.N. Bronsted and T.M. Lowry, 1923)

Acid = a substance that donates a proton, H+ (proton donor) Base = a substance that accepts a proton (proton acceptor) An acid-base rxn is the transfer of a proton from an acid to a base.

B-L acid-base rxns can be described in terms of conjugate acid-base pairs

p. 350

1)

H2O + HF
base1 acid 2

H 3 O+ +
acid1

Fbase2

2) NH3
base1

+ H2O
acid 2

NH4+ + OHacid1 base2

Acid
HCl H2CO3 HPO42HSO3NH4+ CH3COOH

Conj. Base
__________ __________ __________ __________ __________ __________

Base
NH3 SO42SO2PH3 I-

Conj. Acid
__________ __________ __________ __________ __________

3. Lewis Theory (Gilbert N. Lewis, 1923)

Acid = any species that can accept a share in an electron pair. Base = any species that can make available, or donate, a share in an electron pair

Autoionization of water
H2O() H+(aq) + OH-(aq)

ion product constant: *Kw = [H+][OH-] = 1.0 x 10-14

at 25oC

*valid for aq solns and pure water

[H+] = [OH-]

soln is neutral

[H+] = [OH-] = Kw = 1.0 x 10-7 M [H+] > [OH-] [H+] < [OH-] soln is acidic soln is basic

A. Indicate whether soln is acidic, basic or neutral

1. [H+] = 2.4 x 10-5 M 2. [OH-] = 3.0 x 10-9 M

B. Calculate the [OH-] when [H+] = 2.45 x 10-6 M

H+ = a simple proton with no surrounding valence electron = small positively charged particle interacts strongly with the lone pair electrons of water molecules to form hydrated ion H + + :O-H H3O+ H

H+ and H3O+: interchangeably used to represent the hydrated proton 2H2O() H3O+(aq) + OH-(aq)

Kw = [H3O+][OH-] at 25oC = 1.0 x 10-14

For convenience in representing small concentrations of H+ or OH-, the p function was introduced: pH = -log [H+] pOH = -log [OH-] pCa = -log [ __ ] pF = -log [ __ ]

pKw = 14 = pH + pOH
Acidic Basic Neutral pH value < 7.00 > 7.00 = 7.00

Strong Acid
-strong electrolyte, completely ionizes soln. -readily gives up proton binary HCl HBr HI ternary HNO3 H2SO4 HClO4 HClO3 (uncommon) in

Strong Base
-strong electrolyte, completely ionizes in soln. -readily accepts proton 1. Ionic hydroxides of alkali metals: Most common : NaOH, KOH Uncommon: LiOH, RbOH, CsOH 2. Alkaline earth metals : except for Be 3. Oxide ion, O2-: NaO, CaO 4. Ionic hydrides and nitrides: N3-, H-

O2-(aq) + H2O() H-(aq) + H2O() N3-(aq) + 3H2O()

2OH-(aq) H2(g) + OH-(aq) NH3(aq) + 3OH-(aq)

Sr(OH)2 is a strong base, so it is 100% dissociated. Sr(OH)2(aq) Sr2+(aq) + 2OH(aq) 0.0105 M 0.0105 M 2(0.0105) M So [Sr2+] = 0.0105 M and [OH-] =0.0210 M (the strong base is the only source of [OH-])

HClO3 is a strong acid, so it is 100% ionized. HClO3(aq) + H2O(l) H3O+(aq) + ClO3(aq) 0.0105 M 0.0105 M 0.0105 M So [H3O+] = 0.0105 M and [ClO3] = 0.0105 M (the strong acid is the only source of [H+])

Strong acid
HCl HBr HI HNO3

Ka
103.9 105.8 1010.4 101.4

1. What is the pH of a 0.040 M HClO4? 2. pH of HNO3 is 3.45, what is [H+]? 3. What is pH of 0.011 M Ca(OH)2?

Weak Acid/Base
= partially ionizes in soln The extent to which the weak acid ionizes is expressed through the equilibrium constant for the ionization reaction. ( the strength of the acid)

Ka, acid dissociation constant

HA(aq) H+(aq) + A-(aq)

Ka = [H+][A-] [HA]

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Weak Bases

Two categories of weak bases

1. Neutral substance: contains an atom with a lone pair of electrons that can serve as a proton acceptor. Ex: Nitrogen-containing cpds 2. Anions of weak acids Ex: ClO- (source is a salt, NaClO) ClO-(aq) + H2O HClO(aq) + OH-(aq)

Kb = 3.3x10-7

Kb, base dissociation constant

B(aq) + H2O() Kb = BH+(aq) + OH-(aq) [BH+][OH-] [B]

(Kb always refers to the equilibrium in which a base reacts with H2O to form the conj acid and OH-)

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 Monofunctional (HCl, HOAc) : Ka (NaOH, NH3) : Kb Polyfunctional (H2SO4, H3PO4): Ka1, Ka2 (Kb1, Kb2 Extent of dissociation is measured thru the magnitude of its Ka (dissociation constant of the acid) or its Kb (dissociation constant of the base).

What is the pH of a 0.25 M HF? HF 0.25M -x 0.25-x H+(aq) + 0 x x F-(aq) 0 x x

I C E

Ka = [H+][F-] HF

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Ka = 7.2 x 10-4 7.2 x 10-4 X2 0.25 x x2 = 1.8 x 10-4 7.2 x 10-4x =

x2 + 7.2 x 10-4x 1.8 x 10-4 = 0

Solving quadratic equations: For a general quadratic equation y = x2 + bx + c, x2 + bx + c = 0 the roots of the equation (i.e., the value of x when the equation is zero, y = 0), the real value (+) = 0.013 M [H+] = [F-] = 0.013 M

% ionization
[H+] x 100 [HF]i 0.013 M x 100 = 5.2 % 0.25 M

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What is the pH of a 0.10 M HOAc?

I C E HOAc 0.10M -x 0.10-x H+(aq) 0 x x + OAc-(aq) 0 x x

Ka = [H+][OAc-] [HOAc]

Ka = 1.8 x 10-5 x2 0.100 x Simplify eqn, the small value of Ka indicates that the acid is only slightly ionized, such that x <<<0.100 or 0.100 x ~ 0.100 = x = 1.8 x 10-5(0.100) = 1.3 x 10-3 M 1.8 x 10-5

% ionization = 1.3 x 10-3 M x 100 0.100M = 1.3 % assumption is valid when : x/initial < 5%

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NH3(aq) + H2O(l) 0.25 x M

NH4+(aq) + OH(aq) xM xM

Kb = [NH4+][OH- ] (x)2 [NH3] = (0.25 - x) = 1.8 x 105 assume x << 0.25 so x2 = 4.5 x 106 [OH-] = x = 2.1 x 103 M assumption correct: 2.1 x 103 M << 0.45 M % = 2.1 x 10-3 0.25 x 100% = 0.84%

A soln was prepared by adding solid *NaClO to enough water to make a 2.00liter soln. If pH of the prepared soln is 10.50, how many moles of NaClO were added.
*Sodium hypochlorite: bleach, disinfectant

How many moles of KCN should be dissolved in 3.0L if pH of the soln is 11.30?

KCN : used in the extraction of gold and silver from ores, insecticide, fumigant

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Appln: Calcn of Ka from % ionization

In 0.0100 M soln HOAc is 4.2% ionized. Calc its Ka.

Polyprotic Acid
= acid that contains more than one ionizable hydogen atom per formula unit H2SO4 H3PO4 H2C2O4

Stepwise ionization of polyprotic acid

H2C2O4 HC2O4H+ + HC2O4H+ + C2O4-2 Ka1 = 5.9 x 10-2 Ka2 = 6.4 x 10-5

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Calculate all species present in 0.100 M H2C2O4

H2C2O4 I 0.100M C -x E 0.100-x H+ + HC2O40 0 +x +x x x x2 0.100-x
Ka1 = 5.9 x 10-2

5.9 x 10-2 =

Solve by quadratic eqn, Ka1 is too large to neglect x relative to 0.100 M x2 + (5.9 x 10-2)x - 5.9 x 10-3 = 0 x = [H+]1st = [HC2O4-] = 0.053 M HC2O40.053-y H+ + C2O4-2 0.053 +y y Ka2 = (0.053 + y)(y) 0.053 -y
Ka2 = 6.4 x 10-5

6.4 x 10-5 = (0.053 + y)(y) 0.053 y

y << 0.053, so

6.4 x 10-5 = (0.053)(y) 0.053 +] 2-] = 6.4 x 10-5 M (=Ka2) y = [H 2nd = [C2O4 [H+]1st = 0.053 M >> [H+]2nd = 6.4 x 10-5 M

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Relationship of Ka and Kb
HOAc H+(aq) + OAc-(aq) OAc- + H2O HOAc + OHH2O H+ + OHKa = 1.8 x 10-5 Kb = ?

Kw = Ka x Kb Kw KaHOAc

Therefore KbOAc- =

Pyridine, C5H5N has a Kb value of 1.5 x 10-9. What is the Ka of C5H5NH+ ? If Ka for HNO2 is 5.1 x 10-4, what is Kb for NO2-?

Pyridine : used as pesticide, toxic by ingestion and inhalation (tolerance is 5 ppm in air), explosive in air at 1.8 2.4%

Acid-Base Properties of Salt Solns

Salt : ionic cpd with a cation other than H+ and an anion other than OH- or O2Dilute solns of soluble salts are assumed to completely ionize in water

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The acid/base properties of salt solns are due to the behavior of their cations and anions
Aqueous solns produced from salts of: 1. a strong acid and a strong base is neutral 2. a strong acid and a weak base is acidic 3. a weak acid and a strong base is basic 4. a weak acid and a weak base will depend on the extent of hydrolysis of each ion.

1.Salts of strong acids and strong bases. Ex: KNO3 salt of nitric acid and potassium hydroxide CaSO4 salt of sulfuric acid and calcium hydroxide

2. Salts of weak acids and strong bases.

Ex:

NaF
salt of hydrofluoric acid and sodium hydroxide

Ba(NO2)2 salt of nitrous acid and barium hydroxide

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3. Salts of strong acids and weak bases.

Ex: (NH4)2SO4 salt of sulfuric acid and aqueous ammonia C5H5NHCl pyridiniumCl salt of hydrochloric acid and pyridine Al(NO3)3 (Al3+ + H2O Al(OH)2+ + H+)

4. Salts of weak acids and weak bases.

Ex:

(NH4)2CO3
salt of carbonic acid and aqueous ammonia

CH3NH3F methylammoniumF
salt of hydrofluoric acid and methylamine pH depends on the extent of hydrolysis of each ion

1. Which is more acidic? a) b) c) d) NaNO3, Fe(NO3)3 KBr, KBrO CH3NH3Cl, BaCl NH4NO2, NH4NO3

2. List the ff solns in order of increasing pH 0.10M Co(ClO4)2, RbCN, Sr(NO3)2, KOAc

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Predict whether the salt of Na2HPO4 will form an acidic or basic soln on dissolution in water.

Common Ion Effect

HOAc H+ + OAc-

What happens if a salt, NaOAc is added to the HOAc soln?

In general, the dissociation of a weak electrolyte is decreased by adding to the soln a strong electrolyte that has an ion in common with the weak electrolyte.

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1. What is the pH of a soln made by adding 0.30 mol of HOAc and 0.30 mole of NaOAc to enough water to make 1.0 L of soln? 2. Calculate the [F-] and pH of a soln containing 0.10 mol HCl and 0.20 mol HF in 1.0 L.

Buffer
A soln that resists change in pH when a smallamount of an acid or base is added or when the soln is diluted. Useful in maintaining the pH for a reaction at an optimum value Consists of a mixture of a weak acid and its conj base or a weak base and its conj acid at predetermined concs or ratios.

Which of the following solns are buffer systems? a) KH2PO4/H3PO4 b) NaClO4/HClO4 c) C5H5N/C5H5NHCl (pyridine, Kb= 1.7x10-9) d) KF/HF e) KBr/HBr f) Na2CO3/NaHCO3

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Henderson-Hasselbalch Eqn
pH = pKa + log [conj base] [acid] pOH = pKb + log [conj acid] [base]

Buffer capacity,
Measure of how well a buffered soln resists changes in pH when strong acid or base is added = no of moles of acid(base)/pH unit change highest when ?

Buffer Range
= 2 pH range = the maximum range to which a buffer soln should be exposed effective buffer range HOAc/NaOAc 3.7 5.7 8.3 10.3 NH3/NH4Cl

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 A weak acid with Ka = 1.0 x 10-5 was used to prepare a buffer.

What is the pH of a buffer that is 0.12 M in benzoic acid and 0.20 M in sodium benzoate? Ka = 6.5 x 10-5

1. Calculate the pH of a buffer soln prepared by dissolving 12.51 g NaB (121.135) and 4.55 g HB (157.596) in 1.00 L water. Ka,HB = 8.5 x 10-9

2. If we add 12.0 mL of 1.00 M HCl to the above soln, what will be its new pH?

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Describe how you would prepare a phosphate buffer with a pH of about 7.40 Given: H3PO4 H2PO4HPO42H2PO4HPO42PO43Ka1= 7.5 x 10-3 Ka2 = 6.2 x 10-8 Ka3 = 4.8 x10-13

Other buffer soln preparation

Buffers can also be prepared by adding carefully measured quantity of strong base to a soln of a weak acid (or strong acid to a weak base)
AS LONG AS THE WEAK ACID OR WEAK BASE REMAINS IN EXCESS.

Examples:
1. Na+OH- + HOAc I 0.1 0.2 C -0.1 -0.1 E 0 0.1 OAc- + H2O 0 + 0.1 0.1

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