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CH 10
CH 10
•Bronsted - Lowry: acids are proton donors, bases are proton acceptors (this is the usual
treatment of acid and base reactions in aqueous solution)
• also applicable to non-aqueous reactions, eg. gas phase reaction:
H +
.. .. - H
.. H + : N
:Cl H :Cl:
.. + H N H
H H
•identify acid(s) and base(s); note formation of hydroxide (OH ), a strong base -
• terminology:
• monoprotic acids: single proton donors, eg. HCl, HNO , acetic acid 3
(Table 10.2)
• likewise, mono- , polyprotic bases
• 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-
•note absence of H +
transfer and of water
• Lewis acids generally have vacant orbitals
10.2 Acids & Bases in Aqueous Solution: the Bronsted – Lowry Scheme
add 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
•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
• 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
• autoionization:
K[H2O] = Kw = [H+][OH-]
Kw = ion-product constant
Kw = 1 x 10-14 at 25°C (Table 10.1)
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 (or, H O ) is the strongest proton donor that can exist in water; similarly OH strongest
+
3
+ -
• eg.
HNO 3 (aq) + H 3O(l) → H 3O + (aq) + NO -3 (aq)
•most common strong bases, metal hydroxides, eg. NaOH, KOH, Ca(OH) ; fully dissociated 2
≠ [OH-]
• in acidic solution, [H O ] > 1 x 10 M
3
+ -7
• 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+]
Measuring pH
• pH meter (electrode theory in Chap 12)
• 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)
•the larger K , the stronger the acid (note: K ’s of weak acids always < 1 (strong acids, K
a a a
>> 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 K , the stronger the base (note: K ’s of weak bases always < 1 (strong bases, K
b b b
>> 1)
• can be neutral molecules (eg. CH NH ) or anions (eg. CN )
3 2
-
•use NH 4
+
/NH3 conjugate pair as eg.
NH4+(aq) NH3(aq) + H+(aq)
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
•two equilibria are consecutive reactions leading to the overall above, equ’m constant for
equlibria thus added is product of individual equ’m constants
• define: pK a = - 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 pK ’s) a
• two types:
• calculate K or K from initial concentration(s) and measured pH
a b
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)
Ka = = = 1 .3 2 x0-51 ; ∴ p Ka = 4 .8 8
[ C3 H 5O 2 H ] 01. 0
•using K and a known solution, 4 steps; use 0.30 M acetic acid as example (similar to
a
• 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
+
•another example, if stronger acid (formic acid, K = 1.8 x 10 ) and lower initial acid
a
-4
•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 : -
solution
[H + ][C 2 H 3O -2 ] (x)(x)
Ka = = = 5.6 x 10 -10
[C 2 H 3O 2 H ] 0.50 - x
• 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
• 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
• 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+,
a 5 5
6.7 x 10-6; K for acetate ion 5.6 x 10-10)
b
• second equation has the largest equ’m constant, hence its production of
hydronium ion would dominate the first one’s production of hydroxide ion; predict
an acidic solution
• 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
• NB: above example atypical, since buffer concentration high; pH not usually held absolutely
constant on addition of acid or base
[H + (aq.)][A - (aq.)]
K =
a [HA(aq.)]
[ HA(aq.)]
[H + (aq.)] = K
a
[A - (aq.)]
[ -]
pH = pK a + log A
[HA]
• best buffering at pH near pK of conjugate pair, ie.- capacity to "mop up" added acid or
a
base 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
• 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
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 equ’n before the
equivalence point
• as acid becomes weaker, the equivalence point region of the titration curve is less easy to
discern
•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 K process for Na2CO3 (the CO32- to HCO3- step), this generalization falls down
b1
H 2 CO 3 + OH - → HCO -3 + H 2 O
HCO-3 + OH- → CO23 + H O
-
2
• here, first ionization practically complete before second starts (pK 's 6.4 and
a
10.3)
• 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
2 4 3 4
acids H N+CHRCO H , proteins and nucleic acids (polymers)
3 2
Suggested Problems