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Acid Base Reactions

Classification of Acids & Bases

aqueous solutions involving H+(aq) and OH-(aq)

Arrhenius: in water acids increase [H+], bases increase [OH-]

Bronsted - Lowry Acids & Bases

considered as proton-transfer reactions:

HCl(g)
H2O
H + (aq) + Cl - (aq)
as HCl(g) + H 2 O(l) H 3O + (aq) + Cl- (aq)

Bronsted Lowry definition: acids are proton donors, bases are proton acceptors (this is the
usual treatment of acid and base reactions in aqueous solution)

another reaction eg. (a Bronsted base)

NH 3 (aq) + H 2O(l) NH 4+ (aq) + OH - (aq)

To identify acid(s) and base(s); note formation of hydroxide (OH-), a strong base

terminology:

monoprotic acids: single proton donors, eg. HCl, HNO3, acetic acid

polyprotic acids: donors of two or more protons, eg. H2SO4, H3PO4, carbonic acid

likewise, mono- or polyprotic bases are defined in a similar way.

intermediate forms said to be amphiprotic (previously: amphoteric): capable of acting as
either acid (with another base) or base (with another acid), eg. HSO4-, H2PO4-, HCO3-

Lewis Acids & Bases

Lewis acid - an electron pair acceptor (eg. H+)

Lewis base - an electron pair donor (eg. :NH3 and H2O)

more general as to what can be an acceptor



eg. H3N: + BF3 H3N-BF3

note absence of H+ transfer and of water

Lewis acids generally have vacant orbitals

Cationic Lewis Acids (Hydrolysis of Metal Cations)


many metal ions (not the common alkali and akaline earth ions) show acidic properties in
water, explained by Lewis acidity

Chem 59 - 110 (02)


2

positively-charged metal ions, eg. Fe3+, dissolve through hydration, electron donation from
water O to metal

this polarizes O-H bonds of water even more, causes them to dissociate more easily, i.e.-
become more acidic

eg.
Fe(H2O)63+(aq) Fe(H2O)5(OH)2+(aq) + H+(aq)

amphoteric behavior of some metal hydroxides, (those in the middle of the Periodic Table)

non-metal oxides, eg. CO2, SO2, known as acid anhydrides

Group I and II metal oxides, base anhydrides, eg. CaO + H2O Ca(OH)2

10.2 Acids & Bases in Aqueous Solution: the Bronsted Lowry Scheme

Conjugate Acid - Base Pairs (extra)

add H+

NH 3 (aq) + H 2 O(l) NH +4 (aq) + OH - (aq)


base acid conjugate conjugate
acid base
lose H+

these pairs of species related by presence or absence of a proton are conjugate acid-base pairs

generalized: HA and A- or B: and BH+

can be neutral or charged, Table 10.2

warning: charge consistency!

note that in egs. above water has acted as a base in the presence of an acid (eg. HCl, HNO 3)
and as an acid in the presence of a base (eg. NH3), said to be amphiprotic (including
autoionization reaction)

practice recognizing and writing conjugates

Conjugate Acid - Base Strengths (a survey)

arrange acids in order of ability to donate protons, the more readily an acid gives up a proton
(i.e.- the stronger the acid), the less readily does its conjugate base accept a proton (i.e.- the
weaker the conjugate base)

conversely, the stronger the base, the weaker is the conjugate acid

define strong acids: [H3O+] initial concentration of acid



eg. HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)

whereas weak acids: [H3O+] << initial concentration of acid



eg. CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)

conversely, strong base: [OH-] initial concentration of base



eg. O2-(aq) + H2O(l) 2 OH-(aq)

59 - 110 (02), ch 10, Acid Base Equilibria


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and weak base: [OH-] << initial concentration of base



eg. ammonia, above, or CO32-(aq) + H2O(l) HCO3-(aq) + OH-(aq)

acid - base reaction is necessarily a reaction of two conjugate pairs, direction dominated by
stronger acid - base pair:
HCl(aq) + H2O(l) H3O+(aq) + Cl-(aq)
stronger acid stronger base weaker acid weaker base
than H3O+ than Cl- than HCl than H2O

CH3CO2H(aq) + H2O(l) H3O+(aq) + CH3CO2-(aq)


weaker acid weaker base stronger acid stronger base
than H3O+ than CH3CO2- than CH3CO2H than H2O

Table 10.2 gives relative strengths of common acids and their conjugates (note, inverse
rankings)
Later, use this relative information to predict the direction of an acid - base reaction, eg.
page 326-7

The Hydronium Ion & Autoionization of Water

autoionization:

H 2 O(l) H + (aq) + OH - (aq)


[H + ][OH - ]
K =
[ H 2 O]

very little dissociation, [H2O] constant, 55 M

K[H2O] = Kw = [H+][OH-]
Kw = ion-product constant
Kw = 1 x 10-14 at 25C (Table 10.1)

in neutral solution: [H+] = [OH-] = 1 x 10-7 M

note: Kw a constant, regardless of whether solution neutral

The Proton in H O
2

H+ unlikely; more likely is H3O+, hydronium ion or higher order H5O2+ or H9O4+

equation above is more likely:

H 2O(l) + H 2O(l) H 3O + (aq) + OH - (aq)

H+(aq) and H3O+(aq) used interchangably in terminology; Kw unaffected

59 - 110 (02), ch 10, Acid Base Equilibria


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Strong Acids & Bases

H+(or, H3O+) is the strongest proton donor that can exist in water; similarly OH - strongest base
(levelling effect)
strong electrolytes, fully dissociated

most common strong acids: HCl, HBr, HI, HNO3, HClO4, H2SO4

eg.
HNO 3 (aq) + H 3O(l) H 3O + (aq) + NO -3 (aq)

simply calculate [H+] from original concentration of the acid

most common strong bases, metal hydroxides, eg. NaOH, KOH, Ca(OH)2; fully dissociated
some bases stronger than OH-, dissolve to form OH- (eg. O2-, H-, N3-)

Water and the pH Scale


water Ionization Constant, Kw
in pure water, Kw = 1 x 10-14 = [H3O+][OH-]; and [H3O+] = [OH-] = 1 x 10-7 M (at 25oC)
this is a neutral solution
disturb this equilibrium by adding acid or base, Kw = 1 x 10-14 = [H3O+][OH-], but [H3O+]
[OH-]
in acidic solution, [H3O+] > 1 x 10-7 M
in basic solution, [OH-] > 1 x 10-7 M
do Example 10.2

The pH Scale

[H+] in many aqueous solutions of interest is often quite small, expressed in terms of pH:

pH = - log [H+]

note: p as an operator; log10 implied

neutral solution: [H+] = 1 x 10-7 M, pH = 7.0

pH decreases as [H+] increases

pH of some common aqueous solutions, Fig. 10.4

recall, [H+] and [OH-] related by Kw

use of pOH and, autoionization of water:


pH + pOH = - log Kw = 14.00

Measuring pH

pH meter (electrode theory in Chap 12)

59 - 110 (02), ch 10, Acid Base Equilibria


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estimates using colour changes of acid - base indicators, Fig. 10.9


equilibrium: HIn + H O H O+ + In- , and two forms of indicator have different
2 3
colours (note: this is also an acid-base equilibrium)

10.3 Acid & Base Strength (Weak Acids & Bases)

weak acid, partial dissociation:


HA(aq) + H2O(l) H+(aq) + A-(aq)

equilibrium constant = acid-dissociation constant
[H + ][A - ]
Ka =
[ HA ]

the larger Ka, the stronger the acid (note: Kas of weak acids always < 1 (strong acids, Ka >>
1)

examples in Table 10.2

can be neutral molecules (eg. formic acid, HF, HCN and others), cations (eg. ammonium,
NH4+) or anions (eg. H2PO4-)

similarly for weak bases:


B(aq) + H2O(l) BH+(aq) + OH-(aq)

[BH + ][OH ]
Kb =
[ B]

the larger Kb, the stronger the base (note: Kbs of weak bases always < 1 (strong bases, Kb >>
1)

can be neutral molecules (eg. CH3NH2) or anions (eg. CN-)

Connection Between K and K for a Conjugate Pair


a b

use NH4+/NH3 conjugate pair as eg.


NH4+(aq) NH3(aq) + H+(aq)
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)

[NH 3 ][H + ] [NH 4+ ][OH - ]


Ka = ; Kb =
[NH 4+ ] [NH 3 ]

add the above two equilibria, net is:

H 2 O(l) H + (aq) + OH - (aq)

two equilibria are consecutive reactions leading to the overall above, equm constant for
equlibria thus added is product of individual equm constants

59 - 110 (02), ch 10, Acid Base Equilibria


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[NH 3 ][H + ] [NH 4+ ][OH - ]


Ka x K b =
[NH 4+ ] [NH 3 ]
= [H + ][OH - ] = K w

this result is general: for a conjugate pair


Ka x Kb = Kw
example, p. 326-7, of reaction between HF (aq) and CN-(aq) by consideration of relative acid
strengths from Table 10.2

Weak Acid & Base Equilibria on the pH-Scale

rather than using Ka and Kb, express these on the logarithmic pH-scale:

define: pKa = - log Ka (lower, stronger acid) and pKb = - log Kb (lower, stronger base)

(later: simplify by treating all in terms of acid dissociations, only deal with pKas)

from: Ka x Kb = Kw ; hence: pKa + pKb = 14 (at 25oC)

pKas also given in Table 10.2 and Fig. 10.5

10.4 Equilibrium Calculations for Weak Acids & Bases

two types:

calculate Ka or Kb from initial concentration(s) and measured pH

calculate equilibrium concentrations and pH from initial concentrations and known Ka or
Kb

four steps:

write the ionization equilibrium equation

write the equilibrium expression

construct a table as in chapter 9 (initial, change equilibrium concentrations for all species)

solve for unknown (may or may not be quadratic)

Calculating Ka or Kb from Measured pH

using a known solution:



0.10 mol propanoic acid made up to 1.0 L in H2O; measured pH = 2.94
1. write ionization equilibrium:
C3H5O2H (aq) H+(aq) + C3H5O2-(aq)

2. write equilibrium expression:


[H + ][C 3 H 5O -2 ]
Ka = = ?
[HC 3 H 5O 2 ]

3. construct table as in chapter 9:


2.94 = - log [H+]; hence, [H+] = 1.15 x 10-3 M (assume none of this comes from water
ionization)

59 - 110 (02), ch 10, Acid Base Equilibria


7

C3H5O2H (aq) H+(aq) +


C3H5O (aq)
2
-

initial 0.10 M 0 0
change - x M (= - 1.15 x 10-3) + x M (1.15 x + x M (1.15 x
10-3) 10-3)
equilibrium (0.10 - 1.15 x 10-3) 0.10 1.15 x 10-3 M 1.15 x 10-3 M
M

4. substitute equilibrium concentrations in expression


[H + ][C 3 H 5O -2 ] 1.15 x 10-3
2

Ka = = = 1.32 x 10-5 ; pK a = 4.88


[C 3 H 5O 2 H ] 010
.

Calculating Equilibrium Concentrations and pH for Solutions of Weak Acids

using Ka and a known solution, 4 steps; use 0.30 M acetic acid as example (similar to Examples
10.3 and 10.4):

1. write ionization equilibrium:


C2H3O2H(aq) H+(aq) + C2H3O2-(aq)

2. write equilibrium expression:


[H + ][C 2 H 3O -2 ]
Ka = = 1.8 x 10 -5
[C 2 H 3O 2 H ]

3. construct table as in chapter 9:

C2H3O2H(aq) H+(aq) + C2H3O2-(aq)


initial 0.30 M 0 0
change -xM +xM +xM
equilibrium (0.30 - x) M xM xM

4. substitute equm concns in expression


[H + ][C 2 H 3O -2 ] (x)(x)
Ka = = = 1.8 x 10 -5
[C 2 H 3O 2 H ] 0.30 - x

quadratic in x , avoid as long as (0.30 - x) 0.30; start by assuming this, then:

Ka = x2/0.30 = 1.8 x 10-5


[H+] = x = 2.3 x 10-3 M
pH = - log(2.3 x 10-3) = 2.64

now check assumption, also calculate % ionization of acetic acid:
% ionization = (0.0023/0.30)100 = 0.77%

59 - 110 (02), ch 10, Acid Base Equilibria


8


as long as < 5%, assumption OK (alternatively, OK if [HA]o 100Ka); if not, solve
quadratic (or, use method of successive approximations, p. 331 & Appendix C)

compare with strong acid (eg. HCl, same amount): pH = - log(0.30) = 0.52

results of above calculations also show that [H+] much lower than [HA] added - properties
reflect this, eg. conductivity

another example, if stronger acid (formic acid, Ka = 1.8 x 10-4) and lower initial acid
concentration (1 mM) given, hence must solve quadratic

similarly for calculating equilibrium concentrations and pH for an aqueous solution of a weak
base, eg. pyridine and ammonia (Example 10.5)

same rules of thumb for when quadratic must be solved

note that calculations first furnish [OH-] and then pOH; convert latter to pH

Acid-Base Properties of Salt Solutions: Hydrolysis

strong electrolytes, dissolve readily, but many have anions and/or cations that react with water,
i.e.- undergo hydrolysis

eg. anions from weak acids produce OH-:

A-(aq) + H2O(l) HA(aq) + OH-(aq)



Example 10.6 for sodium acetate (NaCH3COO); pH of 8.9 calculated for 100 mM
solution

cations such as ammonia derivatives dissociate in water to give acidic solutions:

NH4+(aq) NH3(aq) + H+(aq)



eg. exercise: pH of 0.50 M aqueous ammonium chloride?

1. write ionization equilibrium (see above):

2. write equilibrium expression:


[H + ][NH 3 ]
Ka = +
= 5.6 x 10 -10 (Table 10.2)
[NH 4 ]

3. construct table as in chapter 9:

NH4+(aq) NH3(aq) + H+(aq)


initial 0.50 M 0 0
change -xM +xM +xM
equilibrium (0.50 - x) M xM xM

59 - 110 (02), ch 10, Acid Base Equilibria


9

4. substitute equm concns in expression


[H + ][C 2 H 3O -2 ] (x)(x)
Ka = = = 5.6 x 10-10
[C 2 H 3O 2 H ] 0.50 - x

quadratic in x , avoid as long as (0.50 - x) 0.50; start by assuming this, then:

Ka = x2/0.50 = 5.6 x 10-10


[H+] = x = 1.7 x 10-5 M
pH = - log(1.7 x 10-5) = 4.8

now check assumption, also calculate % ionization of ammonium cation:
% ionization = (1.7 x 10-5 /0.50)100 = 0.0034%

some generalizations:
1. salts from a strong acid and a strong base - neutral solution
2. salts from a strong base and a weak acid - basic solution
3. salts from a weak base and a strong acid - acidic solution
4. salts from a weak base and a weak acid - solution pH depends on relative extents of
hydrolysis of the two ions

Acid - Base Reactions

more complex solutions: additional solutes


eg. add strong base of known concentration to solution of acid until equivalence point
(stoichiometric amounts of acid and base)
for weak acid - weak base reaction can predict direction of reaction from relative strengths in
Table 10.2
eg. acetic acid plus ammonia:
overall: CH 3CO 2 H(aq) + NH 3 (aq) NH 4+ (aq) + CH 3 CO -2 (aq)
contributing reactions:
CH 3 CO 2 H(aq) + H 2 O(l) H 3O + (aq) + CH 3CO -2 (aq) ; K a = 1.8 x 10 -5
NH 3 (aq) + H 2 O(l) NH 4+ (aq) + OH - (aq) ; K b = 1.8 x 10-5
H 3O + (aq) + OH - (aq) 2 H 2 O(l) ; K = 1 = 1.0 x 1014
Kw
Ka Kb
for overall reaction: K net = = 3.2 x 10 4
Kw
note that the equilibrium for the overall process is favorable due to coupling of unfavorable
ionizations of acid and base with the very favorable union of hydronium and hydroxide ions

59 - 110 (02), ch 10, Acid Base Equilibria


10

Strong Acid - Strong Base Reactions


both completely ionized, solution pH dictated by excess component; if equal molar amounts,
eg.:
H 3O + (aq) + Cl - (aq) + Na + (aq) + OH - (aq) 2 H 2 O(l) + Na + (aq) + Cl - (aq)
net ionic equation: H 3O + (aq) + OH - (aq) 2 H 2 O(l) ; K = 1 K = 1 x 1014
w
equivalence point only at pH 7.00 for these titrations, not all (see weak acids and bases, later)

Strong Acid - Weak Base Reactions


eg. ammonia + HCl

NH 3 (aq) + H 2 O(l) NH 4+ (aq) + OH - (aq) ; K b = 1.8 x 10 -5


H 3O + (aq) + OH - (aq) 2 H 2 O(l) ; K = 1 K = 1.0 x 1014
w

H 3O + (aq) + NH 3 (aq) H 2 O(l) + NH 4+ (aq)


Kb
for overall reaction: K net = = 1.8 x 10 9
Kw
mix equimolar quantities of strong acid and weak base, get quantitiative conversion to
NH +, which forms an acidic solution
4
overall reaction is reverse of acid dissociation of NH +, hence K = 1/K
4 net a
what is the pH at the equivalence point? pH of a solution of that [NH +]
4
Example: 100 mL of 0.10 M HCl plus 50 mL of 0.20 M NH
3
treat as 0.067 M solution of NH Cl , calculate pH of 5.21
4
similarly: organic amine plus HCl

General Approach to These Problems


extension of our general approach to equilibrium calculations
stoichiometric calculation, from strong acid or base reaction (a titration, later)
from quantity of conjugate formed in first stage calculate its concentration
(i.e.- volume correction)
equilibrium calculation to find resulting pH (whether equivalence point or not)

Strong Base - Weak Acid Reactions

59 - 110 (02), ch 10, Acid Base Equilibria


11

eg. weak acid, formic acid + NaOH

HCO 2 H(aq) + H 2 O(l) H 3O + (aq) + HCO -2 (aq) ; K a = 1.8 x 10 -4


H 3O + (aq) + OH - (aq) 2 H 2 O(l) ; K = 1 = 1.0 x 1014
Kw
HCO 2 H(aq) + OH - (aq) H 2 O(l) + HCO -2 (aq)
Ka 1
for overall reaction: K net = = = 1.8 x 1010
Kw Kb

mix equimolar quantities of strong base and weak acid, get quantitiative conversion to
HCO -, which form a basic solution
2
overall reaction is reverse of base association of HCO -, hence K = 1/K
2 net b
what is the pH at the equivalence point? pH of a solution of that [HCO -]
2
Example: 50 mL of 0.10 M NaOH plus 50 mL of 0.10 M HCO H
2
treat as 0.050 M solution of HCO Na , calculate pH of 8.23
2
hence, appropriatness of phenolphthalein as indicator

Weak Acid - Weak Base Reactions


eg. acetic acid plus ammonia at start of chapter
overall: CH 3CO 2 H(aq) + NH 3 (aq) NH 4+ (aq) + CH 3CO -2 (aq)
Ka K b
for overall reaction: K net = = 3.2 x 104
Kw
for equimolar mixture of the two, expect complete conversion to the salt
is resulting solution acidic or basic?
consider hydrolysis of the two conjugate ion partners in the salt:
CH 3 CO -2 (aq) + H 2 O(l) CH 3 CO 2 H(aq) + OH - (aq) ; K b = 5.6 x 10 -10
NH 4+ (aq) + H 2 O(l) NH 3 (aq) + H 3O + (aq) ; K a = 5.6 x 10-10
i.e.- equal tendencies to make the solution acidic and basic, therefore neutral solution
more difficult situation:
50 mL 0.10 M acetic acid plus 50 mL 0.10 M pyridine (an even weaker base than
ammonia)
is solution acidic or basic? (for the conjugates: K for pyridinium ion, C H NH+, 6.7 x
a 5 5
10-6; K for acetate ion 5.6 x 10-10)
b

59 - 110 (02), ch 10, Acid Base Equilibria


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overall: CH 3CO 2 H(aq) + C5 H 5 N(aq) C 5 H 5 NH + (aq) + CH 3CO -2 (aq)


contributing reactions:
CH 3 CO 2 H(aq) + H 2 O(l) H 3O + (aq) + CH 3CO -2 (aq) ; K a = 1.8 x 10-5
C5 H 5 N(aq) + H 2 O(l) C 5 H 5 NH + (aq) + OH - (aq) ; K b = 1.6 x 10-9
H 3O + (aq) + OH - (aq) 2 H 2 O(l) ; K = 1 K = 1.0 x 1014
w

Ka Kb
for overall reaction: K net = = 2.7
Kw
here, in contrast to the ammonium acetate situation, the equilibrium constant is much
smaller and conversion to pyridinium acetate is about 16% (calculation in class; think
about how much dissociation acetic acid alone would undergo, about 10 times less)
consider hydrolysis of the two component conjugate ions:
CH 3 CO -2 (aq) + H 2 O(l) CH 3CO 2 H(aq) + OH - (aq) ; K b = 5.6 x 10-10
C5 H 5 NH + (aq) + H 2 O(l) C 5 H 5 N(aq) + H 3O + (aq) ; K a = 6.7 x 10-6
second equation has the largest equm constant, hence its production of hydronium ion
would dominate the first ones production of hydroxide ion; predict an acidic
solution

Common Ion Effect (also see p. 370-2)


eg. salt of conjugate base added to soln of weak acid decreases [H+], i.e.- increases pH
eg.
C 2 H 3 O 2 H(aq) H + (aq) + C 2 H 3O -2 (aq)

generate common ion from acid - base reaction: dissociation of weak electrolyte decreases due
to addition of strong electrolyte that has an ion in common (Le Chatelier; we will see this later
in the shape of titration curves before the equivalence point; presence of acetate, above, acts to
suppress further dissociation of acid)

Example: calculate pH of 2.67 for 0.25 M acetic acid, pH of 4.35 of same in presence of 0.10
M sodium acetate

for a weak base, common ion lowers pH, eg.


NH 3 (aq) + H 2 O(l) NH 4+ (aq) + OH - (aq)

59 - 110 (02), ch 10, Acid Base Equilibria


13

10.5 Buffer Solutions

mixture of weak acid - base conjugate pairs


resists change in pH due to added H+ or OH- (will see later with titration curves)
Example: compare addition of strong acid to water with addition to acetate buffer
1.0 mL of 1.0 M HCl added to 1.0 L water or to 1.0 L of acetic acid/sodium acetate
buffer in which [CH CO H] = 0.70 M, [CH CO -] = 0.60 M. Calculate pHs
3 2 3 2
calculate pH of HCl in water = 3.0; pH of buffer 4.68, same with added HCl
this is the buffering effect
opposite example shown in Figure 10.12

do Exercises 10.7 & 10.8


analogous example: 0.50 L of a buffer composed of 0.50 M formic acid and 0.70 M sodium
formate; pH before and after adding 10.0 mL of 1.0 M HCl? (formic acid K = 1.8 x 10-4)
a

NB: above example atypical, since buffer concentration high; pH not usually held absolutely
constant on addition of acid or base

General Expressions for Buffer Solutions


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

[H + (aq.)][A - (aq.)]
K
a [HA(aq.)]

[ HA(aq.)]
[H + (aq.)] = K
a
[A - (aq.)]

take (-logarithm) of each side to get:


key equation: Henderson - Hasselbalch

[ -]
pH = pK a + log A
[HA]

NB: at [base] = [acid], pH = pK , hence the importance and utility of pK s


a a

59 - 110 (02), ch 10, Acid Base Equilibria


14

best buffering at pH near pK of conjugate pair, ie.- capacity to "mop up" added acid or base
a
best
capacity also increased by concentration of conjugate pair
important properties of a buffer are its pH and capacity

quantitative aspects:
use of the equation to calculate pH
use of the equation to prepare buffers of known pH, Exercise 10.10

note: from the equation it is the mole ratio of the conjugate pair that is important, not their
absolute concentrations; hence, pH of a buffer does not change with dilution (but capacity
does)

could equally use K or K for these buffering equilibria but since Henderson Hasselbalch
a b
equation is defined in terms of pK it is convenient and simpler to treat all of these acid base
a
equilibria as acid dissociations

10.6 Acid - Base Titration Curves

pH as a function of added strong base or acid, not just at the equivalence point
especially when a weak acid or base titrated with a strong base or acid, respectively

Strong Acid - Strong Base Titrations


eg. Fig. 10.13, HCl and NaOH
rapid change through equivalence point for small additions of base
excess ion dictates solution pH
eg. 100.0 mL of 0.10 M HCl + 0.10 M NaOH, stages of titration, p. 342-3

Weak Acid - Strong Base Titrations


eg. acetic acid plus NaOH, Fig. 10.14
four regions of interest:

59 - 110 (02), ch 10, Acid Base Equilibria


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1. pH before the titration begins, the weak acid solution itself (pH = 2.87 for 0.10 M
acetic acid)
2. pH at the mid-point of the titration, the pK (for acetic acid, 4.74); near mid-point,
a
shallow slope, i.e.- relatively insensitive to added strong acid or strong base =
buffering region
3. pH at the equivalence point; here basic due to hydrolysis of conjugate base of weak
acid
4. pH when base added beyond the equivalence point
Example 10.11
steps in calculations:
stoichiometric calculation to give concentrations of conjugate pair
equilibrium calculation, usually with Henderson - Hasselbalch equn before the
equivalence point
as acid becomes weaker, the equivalence point region of the titration curve is less easy to
discern

Weak Base - Strong Acid Titrations


eg. ammonia plus HCl; acidic end-point, hence, methyl red appropriate indicator

10.7 Polyprotic Acids & Bases

more than one H+ can dissociate, eg. (all aq)

H2SO3 H+ + HSO3- ; Ka1 = 1.7 x 10-2 ; pKa1 = 1.8


HSO3- H+ + SO3-2 ; Ka2 = 6.4 x 10-8 ; pKa2 = 7.2
similarly phosphoric acid: Ka1 = 7.5 x 10-3 ; Ka2 = 6.2 x 10-8 ; Ka3 = 3.6 x 10-13 (pKas 2.1, 7.2,
12.4, respectively)

note: second dissociation much weaker (more difficult to remove second positive charge from
a molecule already negative), typically 104 106 times weaker (4 6 log units, i.e.- pH/pK
units)

in determining solution pH of a polyprotic acid (fully protonated form) or its full conjugate
base (fully deprotonated), it is the first equilibrium which dominates

eg. the Kb1 process for Na2CO3 (the CO32- to HCO3- step), this generalization falls down
when the two pKs are 3 or less units apart

Examples 10.12 and 10.13

Weak Diprotic Acid - Strong Base Titrations

59 - 110 (02), ch 10, Acid Base Equilibria


16

eg. oxalic acid, first equivalence point not easily discerned from graph
carbonic acid detail in Example 10.12, Fig. 10.16
eg. carbonic acid (dissolve CO in water),
2
neutralization stages:

H 2 CO3 OH - HCO -3 H 2 O
HCO-3 + OH - CO 23 + H 2O
-

here, first ionization practically complete before second starts (pK 's 6.4 and 10.3)
a
titration curve shows discrete waves (as long as pK 's not closer than about 3 pH units)
a
other polyprotic acids: H SO , H PO (see Fig. 10.17 for titration with NaOH) , amino acids
2 4 3 4
H N+CHRCO H , proteins and nucleic acids (polymers)
3 2

Suggested Problems

1, 3, 5; 13 67, odd; or, first few odd in each sub-section

59 - 110 (02), ch 10, Acid Base Equilibria