Chapter 7 Acids and Bases

The Nature of Acids and Bases Acid Strength The pH Scale Calculating the pH of Strong Acid Solutions Calculating the pH of weak Acid Solutions Bases Polyprotic Acids Acid-Base Properties of Salts Acid Solutions in Which Water Contributes to the H+ Concentration 7.10 Strong Acid Solutions in Which Water Contributes to the H+ Concentration 7.11 Strategy for solving Acid-Base Problems: A Summary 7.1 7.2 7.3 7.4 7.5 7.6 7.7 7.8 7.9

Arrhenius (or Classical) Acid-Base Definition

An acid is a substance that contains hydrogen and dissociates in water to yield a hydronium ion : H3O+ A base is a substance that contains the hydroxyl group and dissociates in water to yield OH Neutralization is the reaction of an H+ (H3O+) ion from the acid and the OH - ion from the base to form water, H2O. The neutralization reaction is exothermic: H+(aq) + OH-(aq) H2O(l) + ENERGY

More general definition of acids and bases

Hydrating water molecules

Brnsted-Lowry Acid - A substance that can donate a hydrogen ion, e.g. when chloric acid is dissolved in water.
HClO3(aq) + H2O(l) = H3O+(aq) + ClO3-(aq) HClO3(aq) = H+(aq) + ClO3-(aq)

Brnsted-Lowry Base - A substance that can accept a hydrogen

ion, e.g. when ammonia is dissolved in water: H2O(l) + NH3(aq) = NH4+(aq) + OH-(aq) H+ with water note: The Brnsted-Lowry scheme is not limited to aqueous solutions: HCl(in NH3) + NH3(l) = NH4+(in NH3) + Cl-(in NH3)

Acid strength is determined by a competition of H2O and the conjugate base of the acid for H+
HClO3(aq) + H2O(l) = H3 acid base acid O+(aq) + ClO3 base
-(aq)

Figure 7.2: Acid and conjugate base strength

HCl (aq) Cl- (aq) + H+ (aq)

HClO3 (acid) and ClO3- (conjugate base) form a conjugate pair. H3O+ (acid) and H2O (conjugate base) form a conjugate pair. H2O(l) + NH3(aq) = NH4+(aq) + OH-(aq) acid base acid base H2O (acid) and OH- (conjugate base) form a conjugate pair. NH4+ (acid) and NH3 (conjugate base) form a conjugate pair.

Acid Conjugate Acid

Conjugate Base Base

EP 120: Which of the following can act as Brnsted-Lowry acids? Give the formula of the conjugate Brnsted-Lowry base for each (a) Clnot a Brnsted-Lowry acid because it has no hydrogen. (b) HSO4An acid. Conjugate base: SO42(c) NH4+ An acid. Conjugate base: NH3 (d) NH3 An acid. Conjugate base: NH2(e) H2O An acid. Conjugate base: OH-

Amphoteric Molecules - Can Function as either acids or bases, depending on reaction conditions. Water - (a) acts as an acid in donating a hydrogen ion to NH3, (b) acts as a base in accepting a hydrogen ion from HClO3 Hydrogen phosphate ion can act as an acid: HPO42-(aq) + H2O(l) = H3O+(aq) + PO43-(aq) or as a base: HPO42-(aq) + H2O(l) = H2PO4-(aq) + OH-(aq)

Water Dissociates Slightly:

H2O(l) + H2O(l) = H3O+(aq) + OH-(aq) acid base acid base H2O(l) = H+(aq) + OH-(aq) We can express this process of autoionization in terms of an equilibrium constant:
H 3O + OH K= 2 [ H 2O] + K [ H 2O] = K w = H 3O OH 2

Measurements show that the concentration of H+ and OH- are 1.0 x 10-7 M in pure water. Kw =[H3O+][OH-]=(1.0 x 10-7)(1.0 x 10-7)= 1.0 x 10-14 at 25 oC. This relation is always true, independent of adding an acid or base to the water. Remember that H2O(l) does not enter into the equilibrium constant Kw.

[ H 2O] =

n 1000g 1 = = 55.5 V 18.02g L-1 1.00 L

Can assume that concentration of H2O remains constant and can be absorbed into equilibrium constant, Kw.

Aqueous Acid Solution: contains an excess of H3O+ ions over OH- ions.
Strong Acid: Ionizes completely in aqueous solution. Example: HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq) The single arrow indicates that the reaction goes to completion. Other strong acids include HBr, HI, H2SO4, HNO3 and HClO4
EP 121: What is the concentration of

Graphical representation of the behavior of acids of different strengths in aqueous solution. (a) Strong acid. (b) Weak Acid Quantify acid strength by Ka

HA ( aq ) R H + ( aq ) + A - ( aq ) H+ A Ka = [ HA ]

OH-

ions in a

0.10 M solution of HCl? [OH-] = Kw/[H3O+] = 1.0 x 10-14/0.10 = 1.0 x 10-13 M

Table 7.1 Various Ways to Describe Acid Strength Property Ka value Strong Acid Ka is large Weak Acid Ka is small Far to the left [H+] << [HA]o

Six Strong Acids,

Ka too large

to measure accurately Hydrogen Halides HCl HBr HI Oxyacids Hydrochloric Acid Hydrobromic Acid Hydroiodioic Acid

Position of the Far to the right Dissociation equilibrium Equilibrium concentration [H+] ~ [HA]o of H+ compared with original concentration of HA Strength of conjugate base A- much weaker compared with that of base than H2O water

A- much stronger base than H2O

H2SO4 HNO3 HClO4

Sulfuric Acid Nitric Acid Perchloric Acid

Table 7.2: Ka of moderately weak acids to very weak acids Formula HSO4HClO2 HC2H2ClO2 HF HC2H3O2 [Al(H2O)6]3+ HOCl HCN NH4+ HOC6H5 Name Value of Ka 1.2 x 10-2 1.2 x 10-2 1.35 x 10-3 7.2 x 10-4 1.8 x 10-5 1.4 x 10-5 3.5 x 10-8 6.2 x 10-10 5.6 x 10-10 1.6 x 10-10

Hydrogen sulfate ion Chlorous acid Monochloracetic acid Hydrofluoric acid Acetic acid Hydrated aluminum(III) ion Hypochlorous acid Hydrocyanic acid Ammonium ion Phenol

The Conjugate Pairs in Some Acid-Base Reactions

Conjugate Pair
Acid + Base Conjugate Base + Conjugate Acid

Conjugate Pair Water indicated by arrows

Reaction 1 Reaction 2 Reaction 3 Reaction 4 Reaction 5 HF

HCOOH + NH4

H2O CN

F HCOO NH3 HPO42 HSO4

+ + + + +

H3O+ HCN HCO3 H2O N2H62+

+ + +

H2PO4 H2SO4

CO3

OH N2H5+

The equilibrium position in an acidbase reaction

The stronger acid and the stronger base will always react to form the weaker conjugate base and the weaker conjugate acid

Aqueous Basic Solution: contains an excess of OH- ions over H3O+ ions.
Strong Base: Ionizes completely in aqueous solution. Example: H2O(l) + NaOH (aq) -> Na+(aq) + OH-(aq) H2O(l) + NH2-(aq) -> NH3(aq) + OH-(aq) The single arrow indicates that the reaction goes to completion.

EP120a: Predict whether the forward or reverse reaction is favored for the equilibrium

CH3COOH(aq) + SO (aq) R HSO (aq) + CH 3COO (aq)

24 4 -

EP 122: What is the concentration of H3O+ ions in a 0.10 M solution of NaOH? [H3O+] = Kw/[OH-] = 1.0 x 10-14/0.10 = 1.0 x 10-13 M

Because CH3COO- and HSO42- are the stronger base and acid, the reverse reaction will be favored

The Definition of pH
pH = -log10[H3 O+]

EP 123: What

is the pH of (a) pure water, (b) 0.10M HCl, and (c) 0.1M NaOH?

(a)For pure water, [H+] = 1.0 x 10-7 M, so pH = -log10[1.0 x10-7] = 7.00 (b) The pH of 0.10 M HCl is pH = -log10[1.0 x 10-1] = 1.00 (c)The pH of 0.1 M NaOH is pH = -log10(1.0 x 10-14/0.1) = -log10[1 x 10-13] = 13.0

Significant Figures for Logarithms The number of decimal places in the log is equal to the number of significant figures in the original number.

Classification of pH Values
pH < 7 Acidic Solution pH = 7 Neutral Solution pH > 7 Basic Solution
The pH Value of Some Familiar Aqueous Solutions The pH scale is a compact way to represent solution acidity. It involves base 10 logs (log), not natural logs (ln)

Methods for Measuring the pH of an Aqueous Solution

EP 124: Calculating pH
Calculate the pH of an aqueous HNO3 solution that has a volume of 250.mL and contains 0.465g HNO3.
0.465g HNO3 1 mol HNO3 = 7.38 103 mol HNO3 63.01g HNO3

[ HNO3 ] =
(a) pH paper (b) Electrodes of a pH meter

7.38 103 mol HNO3 + = 0.0295M = H 0.250L + pH = -log10 H = 1.530

The Stepwise Dissociation of Phosphoric Acid

Phosphoric acid is a weak acid, and normally only loses one proton in solution, but it will lose all three when reacted with a strong base. The ionization constants are given for comparison. K a1K =a,1 7.2 103 H2PO4-(aq) + H3O+(aq) H3PO4 (aq) + H2O(l)

Ka always decreases for successive H+

Ka2 = 108 K6.3 a,2 H2PO4-(aq) + H2O(l) HPO42-(aq) + H3O+(aq) 13 Ka3 = 4.2 10 K a,3 HPO42-(aq) + H2O(l) PO43-(aq) + H3O+(aq) K a = 1.9 1022 H3PO4 (aq) + 3 H2O(l) PO43-(aq) + 3 H3O+(aq)

Two new definitions

1) pOH = -log10[OH-]

= - log10(Kw/[H+]) = - log10Kw - log10[H+]) = - log10 (1.0 x 10-14) pH = 14.00 - pH

pOH = 14.00 pH 2) It is convenient to express equilibrium constants for acid dissociation in the form

pKa = - log10Ka

The Relationship Between Ka and pKa

Acid Name (Formula) Ka at 25oC pKa

Calculation of the pH of Weak Acid Solutions - A Systematic Approach

EP 125: What is the pH of a solution of 1.00 M nitrous acid, Ka = 4.0 x 10-4? What % of acid is ionized? (1) Identify major species in solution: HNO2 and H2O (2) Which species can generate H+ ions? HNO2(aq) = H+(aq) + NO2-(aq) H2O(aq) = H+(aq) + OH-(aq) Ka = 4.0 x 10-4 Kw = 1.0 x 10-14

Hydrogen sulfate ion (HSO4-) Nitrous acid (HNO2) Acetic acid (CH3COOH) Hypobromous acid (HBrO) Phenol (C6H5OH)

1.02 x 10-2 7.1 x 10-4 1.8 x 10-5 2.3 x 10-9 1.0 x 10-10

1.991 3.15 4.74 8.64 10.00

(3) Is there a dominant species for H+(aq) production? Because Ka >> Kw , can ignore contribution from water.

HNO2(aq) = H+(aq) + NO2-(aq)

Construct the reaction table:

The equilibrium expression is

H+ NO-2 Ka = 4.0104 = [ HNO2 ]

The initial concentration are [HNO2]0 = 1.00 M, [NO2-]0 = 0, [H+]0 = 10-7 M ~ 0

Conc. (M) Initial

HNO2(aq)

H+(aq)

NO2 -(aq)

1.00

HNO2(aq) = H+(aq) + NO2-(aq)

Construct the reaction table:

HNO2(aq) = H+(aq) + NO2-(aq)

Construct the reaction table:

Conc. (M) Initial

HNO2(aq)

H+(aq)

NO2

-(aq)

Conc. (M) Initial

HNO2(aq)

H+(aq)

NO2 -(aq)

1.00

0 x

0 x

1.00

0 x x

0 x x

Change -x

Change -x At equlib 1.00-x

H + x2 NO 2 = K = 4 .0 1 0 4 = 1.0 0 x [H N O 2 ]

We rearrange this equation to yield a second order polynomial:

x 2 + 4 . 0 10 4 x 4 . 0 10 4 = 0 The polynomial is of the form ax
2

For this equation, the solutions are: x = 0.0198, -0.0202 Only the first solution is valid because it leads to all positive concentrations. [H+] = [NO2-] = 0.020 M [HNO2] = 1.00 - 0.020 = 0.98 M

+ bx + c = 0 has the solutions b 2 4 ac 2a b

which x =

Question (a): What is the pH of this solution? pH =-log([H+]) = -log(0.020) = 1.70 Question (b): Were we correct to neglect H+ from the water Yes because [H+]HNO2 >>[H+]w (0.020>> 10-7) Question (c): What % of the acid is ionized? % ionized = ([H+]/[HNO2]0 ) x 100% = (0.020/1.00) x 100% = 2.0 %

Although Ka is independent of molarity, the percent dissociation depends on molarity

fraction ionized = ([H+]/[HNO2]0 ) Ka/[NO2-]

The pH of a Mixture of Weak Acids

EP 126: Calculate the pH of a mixture that is 1.00 M in phenol (Ka = 1.6 x 10-10 and 5.00 M in acetic acid (Ka = 1.8 x 10-5). Major Species in Solution: phenol (HPhe), acetic acid (HAc) and H2O Which Species Can Generate H+ ions? HAc(aq) = H+(aq) + Ac-(aq) KHAc = 1.8 x 10-5 + HPhe(aq) = H (aq) + Phe (aq) KHPhc = 1.8 x 10-10 H2O(aq) = H+(aq) + OH-(aq) Kw = 1.0 x 10-14 Because KAc >> KHPhe >> Kw Can ignore contribution from water and phenol.

HAc(aq) = H+(aq) + Ac-(aq)

Construct the reaction table:

Conc. (M) Initial Change At equlib

HAc(aq)

H+(aq)

Ac -(aq)

5.00

HAc(aq) = H+(aq) + Ac-(aq)

Construct the reaction table:

HAc(aq) = H+(aq) + Ac-(aq)

Construct the reaction table:

Conc. (M) Initial

HAc(aq)

H+(aq)

Ac -(aq)

Conc. (M) Initial

HAc(aq)

H+(aq)

Ac -(aq)

5.00

0 x

0 x

5.00

0 x x

0 x x

Change -x At equlib

Change -x At equlib 5.00-x

Focusing on the Acetic Acid equilibrium:

H + x2 Ac = K = 1.8 10 5 = 5.00 x [H A c ]

Position of phenol equilibrium

EP 127: What

is the molarity of Phe- in the equilibrium discussed in EP 126?

3 H+ Phe- = 9.48 10 + y ( y ) K = 1.6 1010 = 1.00 y [ HPhe]

9.00 x 10-5 1.8 x 10-5 x = x2 x2 + 1.8 x 10-5 x 9.00 x 10-5 = 0 x = .00948, -.00950 . The positive root is the correct choice. pH = -log(.0095) = 2.02

1.00 y 1.00 9.48 103 + y 9.48 103 y= 1.6 1010 = 1.6 108 M 9.48 103

Very little dissociation of HPhe. Very little H+ from HPhe.

Finding the Ka of a weak acid from % dissociation.

EP 128: If the degree of dissociation of 0.10 M

EP 129: Calculate

the pH of a solution of 3.0 x 10-3 M Ca(OH)2(aq)

propanoic acid is 1.1%, what is Ka? We know [H+] = [Pr-], [HPr] = [HPr]0 [H+]

[OH ] = 2 3.0 103 M = 6.0 103 M [H + ] = Kw 1.0 1014 = = 1.7 1012 M [OH ] 6.0 103

Ka =

[H + ][Pr - ] [H + ] ; from dissociation: 0.011 = [HPr] [HPr]0

[H + ] = 0.011 0.10 = .0011 = [Pr ] [HPr] = 0.10 0.0011 = 0.099

pH = log 1.7 1012 = 11.78

( 0.0011) Ka = ( 0.099 )

= 1.2 105

Note: A base doesnt have to contain OH-, it just needs to be able to accept H+, e.g. aqueous ammonia. NH3(aq) + H2O(l) = NH4+(aq) + OH-(aq) B(aq) + H2O(l) = BH+(aq) + OH-(aq) base acid conj. Acid conj. base

EP 130: What

is the pH of 1.5 M Dimethylamine (CH3)2NH (Kb = 5.9 x 10-4).

Conc. (M) Initial Change Equil. DMA 1.5 DMAH+ OH0 0

(CH3)2NH(aq) +H2O(l) (CH3)2NH2+(aq) + OH-(aq)

Kb =

K [BH + ][OH - ] [BH + ] = [OH - ][H + ] = w [B] [B][H + ] Ka K aK b = K w

[H2O] is essentially constant at 55.5M and is contained in Kb. Kb refers to an equilibrium in which a base forms its conjugate acid by removing H+ from water.

(CH3)2NH(aq) +H2O(l) (CH3)2NH2+(aq) + OH-(aq)

(CH3)2NH(aq) +H2O(l) (CH3)2NH2+(aq) + OH-(aq)

Let x be the amount of dimethylamine that has dissociated. Conc. (M) Initial DMA 1.5 DMAH+ OH0 +x 0 +x Conc. (M) Initial

At equilibrium DMA 1.5 DMAH+ OH0 +x x 0 +x x

Change -x Equil.

Change -x Equil. 1.5 - x

x2 1.5 x 4 8.85 10 5.9 104 x = x 2 K b = 5.9 104 = x 2 + 5.9 104 x 8.85 104 = 0; x= OH = 0.030 M , 0.029M only positive root is meaningful
-

Polyprotic Acids
Can give more than one proton per molecule of acid. They do this in a step-wise manner. Example: oxalic acid: H2C2O4(aq) = H+(aq) + HC2O4-(aq) Ka1 = 5.6 x 10-2

[H + ] =

1.0 1014 = 3.3 1013 ; pH = 12.48 0.030

HC2O4-(aq) = H+(aq) + C2O42-(aq)

Ka2 = 5.4 x 10-5

Polyprotic Acids
EP 131: Calculate the pH of 0.050 M Ascorbic Acid,

K a1 =

H2Asc (Ka1 = 1.0 x 10-5; Ka2 = 5.0 x 10-12). Also calculate the concentration of Asc2-. H2Asc H+ + HAscHAsc- H+ + Asc2Simultaneous equilibria. [H+] has same value in both equilibria! Can simplifying assumptions be made?

[H + ][HAsc- ] x2 = 1.0 105 = [H 2 Asc] 0.050 x

0.05 105 1.0 105 x = x 2

Calculate [H+] from Ka1, substitute this value in second x = [H + ] = 7.0 104 ; pH = 3.15 dissociation equilibrium.

x 2 + 1.0 105 x 5.0 107 = 0;

This OK only because K values very different

Ka 2 =

4 [H + ][Asc 2- ] 7.0 10 ( y ) = = 5.0 1012 [HAsc- ] 7.0 104

y = [Asc ] = 5.0 10

12

In some cases, further dissociation of a polyprotic acid can not be neglected

EP 132: Calculate the pH of a 0.10 M sulfuric acid

At equilibrium Conc. (M) Initial

HSO4(aq) H+(aq) SO42-(aq)

solution. H2SO4 (first dissociation complete; Ka2 = 1.2 x 10-2). Major species in solution are H+(aq), HSO4-(aq) and H2O. HSO4-(aq) can dissociate further. HSO4
-(aq)

0.10

0.10 +x

0 +x

Change -x Equil.

H+(aq)

+ SO4

2-(aq)

Examine this equilibrium. Initial concentrations are [H+(aq)]=0.10M, [HSO4-(aq)]=0.10M.

0.10 - x 0.10 + x x

Ka2 =

2( 0.10 + x ) x [H + ][SO 4 ] = 1.2 102 = [HSO 4 ] 0.10 x

x = 9.8 103 [H + ] = 0.010 + 9.8 103 = 2.0 10 2 ; pH = 1.70 If had neglected 2nd dissociation, x = [H ] = 1.0 10 ; pH = 2.00
Zumdahl shows in Example 7.9 that can neglect dissociation of HSO4- for a 1.0M sulfuric acid solution.
+ 2

What species are present in a solution of a polyprotic acid depends on whether the pH is determined only by the acid, or by the presence of another source of H+.
H 2 CO3 (aq) R H + (aq) + HCO3 (aq) K a1 = 4.3 107 2 HCO3 (aq) R H + (aq) + CO3 (aq) K a 2 = 4.8 1011

2 can have H 2 CO3 (aq), HCO3 (aq), CO3 (aq), and H + (aq)

in solution

10

H 2 CO3 R HCO + H
+ HCO3 H K a1 = [ H 2CO3 ]

fraction HCO3 =

HCO3 2 [ H 2CO3 ] + HCO3 + CO3

HCO R CO + H Ka2
2 + CO3 H = HCO3

2 3

+
+ [ H 2CO3 ] = H K a1 HCO3 fraction HCO3 =

[ H 2CO3 ] + 1 +
HCO
3

2 CO3 HCO3

2 CO3 = Ka2 + HCO3 H

1 + H + 1 + Ka2 + K a1 H

Fraction of HCO3- (and other species) determined by pH which can be changed by adding a strong acid such as HCl

Acid-Base Properties of Salts

Salt an ionic compound that dissolves in H2O to give ions. Sometimes the ions can behave as acids or bases. (a) Strong base + weak acid yields a basic salt (pH> 7). NaOac (b) Strong acid + weak base yields an acidic salt (pH< 7). NH4Cl (c) Strong acid + strong base yields a neutral salt (pH= 7). NaCl (d) a-c are general rules that have some exceptions. In each case, do ions react with water to produce H+ or OH-?

EP 133: What

is the pH of a 0.25 M Sodium Acetate (NaAc) solution?

Let x be the amount of acetic acid that is formed by the following reaction: Ac-(aq) + H2O(l) = HAc(aq) + OH-(aq). Conc. (M) Initial Change Equil. Ac0.25 HAc 0 + OH0
The Na+ is a spectator ion and can be ignored in terms of its effect on pH

Ac-(aq) + H2O(l) = HAc(aq) + OH-(aq) Conc. (M) Initial Ac- = 0.25 HAc 0 +x + OH0 +x

Ac-(aq) + H2O(l) = HAc(aq) + OH-(aq) Conc. (M) Initial Ac- = 0.25 HAc 0 +x + OH0 +x x

Change -x Equil.

Change -x Equil.

0.25 - x x

11

K 1.0 1014 = 5.6 1010 Kb = w = K a 1.8 105

5.6 1010 = [HAc][OH - ] x2 = [Ac ] 0.25 x

EP 134: What is the pH of a 0.15 M

given that Kb = 1.8 105 for NH 3 Let x be the amount of H3O+ that is formed by the following reaction: NH4+(aq) + H2O(l) = NH3(aq) + H3O+(aq)
Conc. (M) Initial Change Equil. NH4+(aq) NH3(aq) H+(aq) 0.15 0 0
The Cl- is a spectator ion and can be ignored in terms of its effect on pH

ammonium chloride (NH4Cl) solution?

1.4 1010 5.6 1010 x = x 2 x 2 + 5.6 1010 x 1.4 1010 = 0; x = 1.2 105 , 1.2 105
[H + ] = 1.0 1014 = 8.3 1010 ; pH = 9.08 1.2 105 If assume 0.25 x 0.25, x = 1.2 105 ; pH = 9.08

NH4+(aq) + H2O(l) = NH3(aq) + H+(aq) Conc. (M) Initial NH4+(aq) NH3(aq) H+(aq) 0.15 0 x 0 x

NH4+(aq) + H2O(l) = NH3(aq) + H+(aq) Conc. (M) Initial NH4+(aq) NH3(aq) H+(aq) 0.15 0 x x 0 x x

Change -x Equil.

Change -x Equil. 0.15-x

K a for reaction is K w K b = 1.0 1014 1.8 105 = 5.6 1010 5.6 10

10

Acid Solutions in Which Water Contributes to [H+]

Previously, we have assumed that the acid is the dominate source of H+ ions. However, in some cases the contribution of H+ ions from water must be taken into account. This situation occurs when pH between 6 and 7 i.e. near neutral. Examples include low concentrations of weak (or even strong) acids, and acids with pKas near 7.

[NH3 ][H + ] x2 = = [NH + 0.15 x 4]

Because K b is so small, x  1 and 0.15 x 0.15. Therefore x2 x2 = 5.6 1010 0.15 x 0.15 x = [H + ] = 9.2 106 ; pH = 5.04

12

Posing the Weak Acid Problem

We have the following four unknowns to solve for: [H+], [OH-], [HA] and [A-] We have the following four equations which govern the concentrations of the above species:

The Solution to the Weak Acid Problem

We now proceed to solve the four simultaneous equations for [H+] by successive elimination of variables. The result is the following cubic equation for [H+].

[H+]3 + Ka[H+]2 (Kw +Ka[HA]0)[H+] KaKw = 0

+ H Kw 2 H+ K [ HA ]0 + w H Finding [H+] using cubic equation can be done in several ways

H+ A Ka = [ HA ]
+ Kw = H OH + H = A + OH

Alternately

acid-base equilibrium water hydrolysis charge balance material balance

Ka =

Use an equation solver (This is the way to go.) Use method of successive approximations

[ HA ]0 = [ HA ] + A

pH of a Very Weak Acid

EP 135: Find
and the pH of a 1.00 L solution containing 3.00 x 10-5 g of vitamin B1, thiamine hydrochloride (HC12H17ON4SCl2, mw = 337.27 g/mol ). For this compound, Ka = 3.4 x 10-7. Use the method of successive approximations. [H+]

[H+]3 + Ka[H+]2 (Kw +Ka[HA]0)[H+] KaKw = 0

let y = [H+] y3 + 3.4 x 10-7y2 (1.0 x 10-14 + (3.4 x 10-7)(8.89 x 10-8))y (3.4 x 10-7)(1.0 x 10-14) = 0 This expression may be simplified to: y3 + (3.4 x 10-7)y2 (4.0 x 10-14)y 3.4 x 10-21 = 0 Using an equation solver [H+]= - 4.2 x 10-7, - 6.0 x 10-7, 1.4 x 10-7

Strategy

(1)Calculate molarity of vitamin B1 (2) [H+] must be between 1 x 10-7 and molarity of vitamin B1 plus +1 x 10-7. [HA]0 = (3.00 x 10-5 / 337.27) / 1.00 L = 8.89 x 10-8 M

y3 + (3.4 x 10-7)y2 (4.0 x 10-14)y 3.4 y x 10-21

result

y3 + (3.4 x 10-7)y2 (4.0 x 10-14)y 3.4 x 10-21

13 x 10-8

-0.67 x 10-21

same same same same same same same

10 x 10-8 11 x 10-8 12 x 10-8 13 x 10-8 14 x 10-8 14 x 10-8 16 x 10-8

-3.0 x 10-21 -2.4 x 10-21 -1.6 x 10-21 -0.67 x 10-21 +0.41 x 10-21 +1.6 x 10-21 +3.0 x 10-21

same

13.5 x 10-8 -0.14 x 10-21

same

14 x 10-8

+0.41 x 10-21

[H+] correct to 2 sig figs is 1.4 x 10-7 pH = 6.85

For correct value of y, value of function = 0.

13

When can this complicated expression be reduced to a simpler one?

+ + 6 If H > 10 , H > 100 K w >> K w 2

An approximate solution for [H+] in the range 10-7<[H+]<10-6

+ H Kw Ka = 2 H+ K [ HA ]0 + w H 2

Ka =

H Kw H + 2 + 2 H K w H HA HA [ ]0 [ ]0 + + H H
+ + + 2 + + -

If [ HA ]0 > 100 9.9 107 1104

[ HA ]0

H+ Kw

Range of usefulness of above expression is

+ 6 107 < H < 10 In this range 2

+ H (1% error) and

[ HA ]0

H A H A H = = = + + H [ HA ]0 H [ HA ] [ HA ]0
This is result you would obtain neglecting water dissociation It is valid for [H+]>10-6

H+ K w 0 + 9.9 107 H

H+ Kw Ka [ HA ]0
+ H

[ HA ]0 K a + K w

EP 135a: Calculate the pH of a 3.0 x 10-5 M ammonium

chloride solution. (Kb for NH3 = 1.8 x 10-5) The reaction is NH4+ + H2O = NH3 + H3O+ Ka = Kw/Kb = (1.0 x 10-14)/(1.8 x 10-5) =5.6 x 10-10
Ka =
+ H + NH 4 H+ 0 2

Strategy for solving for pH in weak acid problems

1)Solve problem neglecting water dissociation. If pH < 6, answer OK 2)If 7 < pH < 6, use the approximation
+ H

+ + 10 5 14 H = Ka NH 4 0 + K w = 5.6 10 3.0 10 + 1.0 10

= 1.6 10

pH = 6.80 Exact solution: 6.80

[ HA ]0 K a + K w

If had neglected water dissociation H + NH3 x2 = = 5.6 1010 K a = + + + NH H NH 4 0 4 0 x H+ = 1.3 107 pH = 6.89

3)Recalculate solving full cubic equation to see if approximation in 2) valid. Will be valid if [HA]0 > 1 x 10-4.

Strong Acid Solutions in Which Water Contributes to [H+]

Usually, a strong acid is the dominant source of H+ ions. However, in some cases the contribution of H+ ions from water must be taken into account. This situation occurs when the concentration of the strong acid is on the order of 10-6 M or less. To solve this problem, we again start with the four equations for the four species.

The Dilute Strong Acid Problem

We have the following four unknowns to solve for: [H+], [OH-], [HA] and [A-] We have the following four equations which govern the concentrations of the above species:

H+ A Ka = [ HA ]
+ Kw = H OH + H = A + OH A [ HA ]0 = [ HA ] +

acid-base equilibrium water hydrolysis charge balance material balance

14

pH of a Low Concentration of a Strong Acid

We can simplify the four equations, because Ka infinity, so [HA] = 0, and [A-] = [HA]0, thus we are left with
+ Kw = H OH + H = [ HA ]0 + OH

EP 136: Find the pH of 2.0 x 10-8 M solution of HCl. This is a

sufficiently dilute solution that the autoionization of water cannot be neglected. However, since the acid is strong, all of the acid may be assumed dissociated. [H+]2 - [HA]0[H+] Kw = 0 Where [HA]0 = 2.0 x 10-8 and Kw = 1.0 x 10-14 Thus the equation to solve is y2 - (2 x 10-8)y 1.0 x 10-14 = 0 y = 1.1 x 10-7, -9.1 x 10-7. We keep the positive root. pH = -log(1.1 x 10-7) = 6.96

water hydrolysis charge balance

We now proceed to solve the two equations for [H+] by elimination of [OH-]. The result is

[H+]2

- [HA]0

[H+]

Kw = 0

Finding [H+] requires that we find the two roots of the above quadratic equation and then selecting the one root that is consistent with physical reality, i.e. leads to all positive concentrations.

Answers to Numerical Problems

EP121: 1.0 x 10-13M EP123 a) 7.00, b) 1.00, c) 13.0 EP125: 1.70, 2.0% EP127: 1.6 x 10-8M EP129: 11.78 EP 131: 3.15, 5.0 x 10-12 M EP 133: 9.08 EP 135: 1.4 x EP 136: 6.96 10-7M, 6.85 EP122: 1.0 x 10-13M EP124: 1.530 EP 126: 2.02 EP 128: 1.2 x 10-5M EP 130: 12.48 EP 132: 1.70 EP 134: 5.04 EP 135a: 6.79

15