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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)
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-
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)
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
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)
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
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 25C (Table 10.1)
The Proton in H O
2
H+ unlikely; more likely is H3O+, hydronium ion or higher order H5O2+ or H9O4+
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)
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-)
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
Measuring pH
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-)
[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-)
two equilibria are consecutive reactions leading to the overall above, equm constant for
equlibria thus added is product of individual equm constants
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)
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)
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
using Ka and a known solution, 4 steps; use 0.30 M acetic acid as example (similar to Examples
10.3 and 10.4):
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
strong electrolytes, dissolve readily, but many have anions and/or cations that react with water,
i.e.- undergo hydrolysis
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
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
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 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
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
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
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
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