GIST 

Anal Chem 10/10/2016

8. MONOPROTIC ACID-
BASE EQUILIBRIA
GIST Analytical Chemistry by Kim, Tae-Young

1. Strong Acids & Bases

: Dilemma in calculating the pH of strong acids & bases
2

 pH of 0.10 M KOH (strong base)?

 Kw = [H+][OH–] = 1.0×10−14

Kw 1.0  1014
[H  ]    1.0  1013 M pH  log[H + ]  13.00
[OH  ] 0.10
 Relation between pH & pOH
pH  pOH   log K w  14.00 at 25C

 pH of 1.0×10−8 M KOH?
Kw 1.0  1014
[H  ]    1.0  106 M pH   log[H  ]  6.00
[OH  ] 1.0 108
► How can the base KOH produce an acidic solution (pH < 7)? → It is impossible!!!

1
GIST Anal Chem 10/10/2016

The cure for the dilemma

3

 We have not considered the contribution of OH– from the ionization of water.
 In pure water, [OH–] = 1.0×10–7 M, which is greater than the amount of KOH added to the solution.

 Systematic treatment of equilibrium

 Step 1: Pertinent reactions. H2O ⇌ H+ + OH–, Kw = 1.0×10−14
 Step 2: Charge balance. [K+] + [H+] = [OH–]
 Step 3: Mass balance. All K+ comes from the KOH, so [K+] = 1.0×10−8 M.
 Step 4: Equilibrium constant. Kw = [H+][OH–] = 1.0×10−14
 Step 5: Count. Three equations & three unknowns ([H+], [OH–], & [K+]).
 Step 6: Solve. Find the pH.

pH of 1.0×10−8 M KOH
4

 Let’s set [H+] = x. Since [K+] = 1.0×10−8 M, the charge balance becomes:
[OH–] = 1.0×10−8 + x
 Putting [OH–] = 1.0×10−8 + x into the Kw equilibrium enables us to solve the problem:
[H+][OH–] = Kw
(x)(1.0×10−8 + x) = 1.0×10−14
x2 + (1.0×10−8)x – (1.0×10−14) = 0
x = 9.6×10−8 M or –1.1×10−17 M
 Rejecting the negative concentration, we conclude that:
[H+] = 9.6×10−8 M → pH = –log[H+] = 7.02
 This pH is reasonable, because 10−8 M KOH should be very slightly basic.

2
GIST Anal Chem 10/10/2016

Calculated pH as a function of concentration of strong

acid or strong base in water
5

 When the concentration is “high” (≥ 10−6 M), pH is

calculated by just considering the added H+ or OH–.
 The pH of 10−5.00 M KOH is 9.00.

 When the concentration is “low” (≤ 10−8 M), pH is 7.00.

 We have not added enough acid or base to change the pH of the
water itself.

 At intermediate concentration (10−6 ~ 10−8 M), the effects

of water ionization & added acid or base is comparable.
 A systematic equilibrium calculation is required.
Calculated pH as a function of conc. of
strong acid or base in water.

2. Weak Acids & Bases

: Not completely dissociated
6

 Acid dissociation constant (Ka) for the acid HA:

 Base hydrolysis constant (Kb) for the base B:

 pK: The negative logarithm of an equilibrium constant.

 pKw = –log Kw , pKa = –log Ka, & pKb = –log Kb

3
GIST Anal Chem 10/10/2016

Conjugate acid-base pair

: Relationship by the gain or loss of a proton
7

Ka = 1.80×10−4
pKa = 3.744

Ka = 6.28×10−5
pKa = 4.202

 As Ka increases, pKa decreases: Smaller pKa means stronger acid.

 Conjugate acid-base pair: Gain of loss of a proton (HA & A– or B & BH).
Ka  Kb  Kw

Weak is conjugate to weak

8

 Weak is conjugate to weak.

 The conjugate base of a weak acid is a weak base: A weak acid (Ka = 10−4 → Kb = Kw/Ka = 10−10).
 The conjugate acid of a weak base is a weak acid: A weak base (Kb = 10−5 → Ka = Kw/Kb = 10−9).

 As HA becomes a weaker acid, A– becomes a stronger base (but never a strong base).

 The greater the acid strength of HA, the less the base strength of A–.

 If HA is strong (such as HCl), its conjugate base (Cl–) is so weak that it is not a base at all in
water.

4
GIST Anal Chem 10/10/2016

How to use Appendix G which lists acid dissociation

constants?
9

 Each compound is shown in its fully protonated form, but names refer to neutral molecules.
 Name: Diethylamine.
 Structure: Diethylammonium ion, (CH3CH2)2NH2+.
 The value of Ka: Ka for diethylammonium ion.

 For polyprotic acids & bases, several pKa values are given.

3. Weak-Acid Equilibria
10

 Find the pH of a solution of the weak acid HA, given the formal concentration (F) of HA &
the value of Ka.
 Reactions: Ka Kw
HA ⇌ H+ + A–, H2O ⇌ H+ + OH–
 Charge balance: [H+] = [A–] + [OH–]
 Mass balance: F = [A–] + [HA]
 Equilibrium expressions:
[H  ][A  ]
Ka  Kw = [H+][OH–]
[HA]
 Four equations & four unknowns ([A–], [HA], [H+], & [OH–]).
 We need to solve a cubic equation!

5
GIST Anal Chem 10/10/2016

A good approximation in a typical weak-acid problem

: [H+] ≈ [A−]
11

 For any respectable weak acid, [H+] from HA will be much greater than [H+] from H2O.
 When HA dissociates, it produces A–.
 When H2O dissociates, it produces OH–.
 If dissociation of HA is much greater than dissociation of H2O, then [A–] >> [OH–].
 So, the charge balance equation reduces to [H+] ≈ [A–].
 This approximation would be poor only if the acid were too dilute or too weak.
 To solve the problem, first set [H+] = x → From the approximation above, [A–] = x.
 The mass balance becomes: [HA] = F – [A–] = F – x
 Thus, the expression for Ka:
[H  ][A  ] x2
Ka  
[HA] F x

Example
: Find the pH of 0.050 M trimethylammonium chloride
12

 We assume that ammonium halide salts are completely dissociated.

 [(CH3)3NH]Cl(s) → (CH3)3NH+(aq) + Cl–(aq)
 We can recognize that triethylammonium ion is a weak acid.
 Its conjugate base, triethylamine is a weak base.
 Cl– has no basic or acidic properties and should be ignored.
 In Appendix G, pKa for triethylammonium ion is 9.799 → Ka = 1.59×10−10.

x2
 1.59  1010
0.050  x
x  2.8  106 M  pH  5.55

6
GIST Anal Chem 10/10/2016

A handy tip
: Approximation
13

 In the previous example, if x comes out much smaller than F (x << 0.050), then we can
neglect x in the denominator.
x2 x2
  1.59  1010
0.050  x 0.050
x = 2.8×10−6 M
 Validation of the approximation
 The approximation solution (x ≈ 2.8×10−6 M) is much smaller than the term 0.050 in the denominator.

 Approximation
 Neglect x in the denominator.
 If x comes out to be less than 1% of F, accept the approximation.

pH of 0.050 0 M (F) of o-hydroxybenzoic acid

(Ka = 1.07×10−3)
14

 For a weak acid: [H  ][A  ] x2

Ka  
[HA] F x
x2
 1.07 103
0.050 0  x
 If we solve this quadratic equation, x = 6.80×10−3
[H+] = [A–] = 6.80×10−3 M → pH = –log x = 2.17
[HA] = F – x = 0.0432 M
 Was the approximation [A–] >> [OH–] ([H+] ≈ [A–]) justified? Yes!
[OH–] = Kw/[H+] = 1.5×10−12 M (<< [A–] = 6.80×10−3 M)
 In a solution of a weak acid, H+ is derived almost entirely from HA, not from H2O.

7
GIST Anal Chem 10/10/2016

Fraction of dissociation, α
15

 Fraction of dissociation (α): The fraction of the acid in the form of A–.

[A  ] x x
α  
[A ]  [HA] x  (F  x) F


 For 0.050 0 M o-hydroxybenzoic acid:

6.8 103 M
α  0.14
0.050 0 M
 The acid is 14% dissociated at a formal concentration of 0.050 0 M.

 Weak electrolytes dissociate more as they are diluted. → Why? Fraction of dissociation of a weak
electrolyte vs. its concentration.

4. Weak-Base Equilibria
16

 The treatment of weak bases is almost the same as that of weak acids.
[BH  ][OH  ]
B + H2O ⇌ BH+ + OH– Kb 
[B]

 We suppose that nearly all OH– comes from the reaction B + H2O, little comes from
dissociation of H2O.
 Setting [OH–] = x, we must also set [BH+] = x.
 F = [B] + [BH+] → [B] = F – [BH+] = F – x

[BH  ][OH  ] x2
α   Kb
[B] F x
 This looks a lot like a weak-acid problem, except that now x = [OH–].

8
GIST Anal Chem 10/10/2016

Typical weak-base problem

: pH of 0.037 2 M Cocaine
17

B + H2O ⇌ BH+ + OH– Kb = 2.6×10−6

0.037 2 − x x x
x2
 2.6 106 → x = 3.1×10−4
0.037 2  x
[H+] = Kw/[OH–] = 3.2×10−11 M → pH = –log[H+] = 10.49
 Fraction of dissociation (α): [BH  ] x 3.110 4
α    0.0083 (0.83% reacted)
[BH  ]  [B] F 0.037 2

Buffer
: A mixture of a weak acid & its conjugate base
18

 A buffered solution resists changes in pH when acids or bases

are added or when dilution occurs.
 There must be comparable amounts of the conjugate acid & base
(within a factor of ~10) to exert significant buffering.

 pH dependence of chymotrypsin activity:

 The pH dependence of the rate of cleavage of an amide bond by the
enzyme chymotrypsion is shown in Fig. 8-3.

 For an organism to survive, it must control the pH of each

subcellular compartment so that each reaction proceeds at the
proper rate. pH dependence of Chymotrypsin activity.

9
GIST Anal Chem 10/10/2016

Mixing a weak acid & its conjugate base

: You get what you mix!
19

 If you mix A moles of a weak acid with B moles of its conjugate base, the moles of acid remain
close to A & moles of base remain close to B.
 Consider an acid with pKa = 4.00 & its conjugate base with pKb = 10.00.
 Fraction of dissociation (α) of a 0.10 M HA  Fraction of association (α) of of a 0.10 M A–
HA ⇌ H+ + A–, pKa = 4.00 A– + H2O ⇌ HA + OH–, pKb = 10.00
x2 x2
 K a  x  3.1 103 M  K b  x  3.2 106 M
F x F x
Fraction of dissociation (α) = x/F = 0.031 Fraction of association (α) = x/F = 3.2 10−5

 Le Châtelier’s principle in buffers

 HA dissociates very little, & adding A– to the solution makes HA dissociates even less.
 A– does not react much with water, & adding extra HA makes A– react even less.

Henderson-Hasselbalch equation
: The central equation for buffers
20

[H  ][A  ]
Ka 
[HA]
[H  ][A  ] [A  ]
log K a  log  log[H  ]  log
[HA] [HA]
 [A  ]
 log[H ]   log K a  log
     [HA]
pH pK a
 Henderson-Hasselbalch equation for an acid: HA ⇌ H+ + A– (Ka)
[A  ]
pH  pK a  log
[HA]
 Henderson-Hasselbalch equation for a base: BH+ ⇌ B + H+, (Ka = Kw/Kb)
[B]
pH  pK a  log pKa applies to
[BH + ] this acid

10
GIST Anal Chem 10/10/2016

Properties of the Henderson-Hasselbalch equation

21

[A  ]
pH  pK a  log
[HA]
[A  ]
 If [A–] = [HA], then pH = pKa: pH  pK a  log  pK a  log1  pK a
[HA]
 Regardless of how complex a solution may be, whenever pH = pKa, for a particular acid, [A–] must equal
[HA] for that acid.
 The volume of a buffer solution is irrelevant to pH, since volume cancels in the log term.

 Effect of [A–]/[HA] on pH:

Example
:A buffer solution of tris(hydroxymethyl)aminomethane
22

 Find the pH of a 1.00-L aq. solution prepared with 12.43 g of tris (FM 121.135) plus 4.67 g
of tris hydrochloride (FM 157.596).

BH+, pKa = 8.072 B, this form is “tris”

 The concentrations of B & BH+ added to the solution are
12.43 g/L 4.67 g/L
[B]   0.102 6 M [BH + ]   0.029 6 M
121.135 g/mol 157.596 g/mol
 Assuming that what we mixed stays in the same form:
[A  ] 0.102 6
pH  pK a  log  8.072  log  8.61
[HA] 0.029 6

11
GIST Anal Chem 10/10/2016

Effect of Adding acid to a buffer: pH after adding

12.0 mL of 1.00 M HCl to the previous solution?
23

 Key: When a strong acid is added to a weak base, they react completely to give BH+.

 The number of moles of H+ added: (0.012 0 L)(1.00 mol/L) = 0.012 0 mol

 This much H+ consumes 0.012 0 mol of B to create 0.012 0 mol of BH+:
B + H+ → BH+
Tris From HCl

Initial: 0.102 6 0.012 0 0.029 6

Change: 0.012 0 0.012 0 0.012 0
Equilibrium: 0.090 6 - 0.041 6
moles of B 0.090 6
pH  pK a  log +
 8.072  log  8.41
moles of BH 0.041 6
 The pH of buffer does not change very much when a limited amount of strong acid or base is added.

Why does a buffer resist changes in pH?

: The buffer consumes the added acid or base
24

 In the previous slide, we see that addition of 12.0 mL of 1.00 M HCl changed the pH from
8.61 to 8.41.
 On the other hand, addition of 12.0 mL of 1.00 M HCl to 1.00 L of pure water would have lowered
the pH to 1.93.

 A buffer resists changes in pH because the strong acid or base is consumed by B or BH+.
 If you add HCl to tris, B is converted into BH+.
 If you add NaOH, BH+ is converted into B.

 As long as you don’t use up B or BH+ by adding too much HCl or NaOH, the log term of the
Henderson-Hasselbalch equation does not change much & pH does not change much.

12
GIST Anal Chem 10/10/2016

Example
: Calculating how to prepare a buffer solution
25

 How many milliliters of 0.500 M NaOH should be added to 10.0 g of tris hydrochloride to
give a pH of 7.60 in a final volume of 250 mL?
 The moles of tris hydrochloride are (10.0 g)/(157.596 g/mol) = 0.063 5 mol.
Reaction with OH– : BH+ + OH– → B
Initial: 0.063 5 x -
Equilibrium: 0.063 5 ‒ x - x
 We use the Henderson-Hasselbalch equation to find x, because we know pH and pKa.
moles of B x
pH  pK a  log  7.60  8.072  log
moles of BH +
0.063 5  x
x
0.472  log  x  0.016 0 mol
0.063 5  x
 This many moles of NaOH is contained in (0.016 0 mol)/(0.500 mol/L) = 0.032 0 L = 32.0 mL

How to prepare a buffer in real life!

26

 A calculation could be wrong because of
the following reasons:
 Activity coefficients were not considered.
 The temperature might not be 25°C, for which
pKa is listed.
 The approximations [HA] = FHA & [A–] = FA–
could be in error.
 pKa listed for tris in your favorite table is
probably not exactly what you would measure.
 Other ions besides the acid & base species
affect pH by ion-pairing reactions with acid &
base species.
 Prepare a tris buffer of pH 7.60 in real life.
 Weight out 0.100 mol of tris hydrochloride &
dissolve it in a beaker containing about 800 mL
of water.
 Place a calibrated pH electrode in the solution
& monitor the pH.
 Add NaOH solution until the pH is exactly 7.60.
 Transfer the solution to a volumetric flask &
wash the beaker a few times.
 Add the washings to the volumetric flask.
 Dilute to the mark & mix.

13
GIST Anal Chem 10/10/2016

Buffer capacity (β)

27

 Buffer capacity (β): A measure of how well a solution resists

changes in pH when strong acid or base is added.
dCb dC
β  a
dpH dpH
where Ca & Cb are the number of moles of strong acid & base per liter needed
to produce a unit change in pH.
 The greater the buffer capacity, the more resistant the solution is to pH 0.100 F HA
change. (pKa = 5.00)

 A buffer is most effective in resisting changes in pH when pH =

pKa (that is, when [HA] = [A–]).
 In choosing a buffer, seek one whose pKa is as close as possible to the
desired pH.
 The useful pH range of a buffer is usually considered to be pKa ± 1 pH unit. (a) Cb vs. pH & (b) buffer capacity vs. pH.

Table 8-2
:Buffer pH depends on ionic strength & temperature
28

 The correct Henderson-Hasselbalch equation includes activity coefficients.

[A  ]γ A
pH  pK a  log
[HA]γ HA
 The most important reason why the calculated pH of a buffer is not equal to the observed pH: The ionic
strength of a buffer is not 0, so activity coefficients are not 1.
 Table 8-2 lists pKa values for common buffers widely used in biochemistry at μ = 0 & μ = 1.
 When a 0.5 M stock solution of phosphate buffer at pH 6.6 is diluted to 0.05 M, the pH rises to 6.9.

 Buffer depends on temperature, as indicated in the last column of Table 8-2.

 Tris has an exceptionally large dependence, ‒ 0.028 pKa units per degree, near room temperature.
 A solution of tris with pH 8.07 at 25°C → pH ≈ 8.7 at 4°C & pH ≈ 7.7 at 37°C.

14
GIST Anal Chem 10/10/2016

When what you mix is not what you get

: In dilute solution or at extremes of pH
29

 In dilute solution or at extremes of pH, the [HA] ≠ F & [A–] ≠ F.

 Suppose we mix FHA moles of HA & FA– moles of the salt Na+A–.
 Mass balance: FHA + FA– = [HA] + [A–]
 Charge balance: [Na+] + [H+] = [OH–] + [A–]
 The substitution [Na+] = FA– leads to the equations
[HA] = FHA – [H+] + [OH–]
[A–] = FA– + [H+] – [OH–]
 If FHA or FA– is small, or if [H+] or [OH–] is large, then the approximations [HA] ≈ FHA & [A–] ≈ FA– are
not good.
 In acidic solutions, [H+] >> [OH–] , so [OH–] can be ignored in the equations above.
 In basic solutions, [H+] can be ignored.

Example
: A dilute buffer from a moderately strong acid
30

 Find the pH if 0.010 0 mol of HA (pKa = 2.00) & 0.010 0 mol of A– are dissolved in water to
make 1.00 L of solution?
 The solution is acidic (pH ≈ pKa = 2.00), so we neglect [OH–] in this calculation.
HA ⇌ H+ + A–
0.010 0 ‒ x x 0.010 0 + x
 
[H ][A ] ( x)(0.010 0  x)
Ka    102.00
[HA] (0.010 0  x)
x = 0.004 14 M → pH = log[H+] = 2.38 (≠ 2.00)
 [HA] & [A–] are not what we mixed:
[HA] = FHA – [H+] = 0.005 86 M & [A–] = FA– + [H+] = 0.014 1 M
 In this example, HA is too strong & the concentrations are too low for HA & A– to be equal their formal
concentrations.

15