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F15 CHEM 2880

X. Acid/Base Chemistry
Three definitions:
1) Arrhenius: Acid increases [H+]; Base increases [OH]
2) Brnsted-Lowry: Acid donates a proton; Base accepts a proton

3) Lewis: Acid electron-pair acceptor; Base electron-pair donor


Brnsted-Lowry includes conjugates, e.g.,
HCl(aq) + H2O(l) H3O+(aq) + Cl(aq); Ka
CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq); Ka
NH3(aq) + H2O(l) NH4+(aq) + OH(aq); Kb

a) Water behaves as both an acid and a base


H2O(l) + H2O(l) H3O+(aq) + OH(aq)
weak acid weak base

conjugate acid conjugate base

OR
H2O(l) H+(aq) + OH(aq)
water is a very weak acid and a very weak base
autoprotolysis or autoionization
=
Kw

aH + aOH
H + OH
= a=
a
H + OH
a H 2O

value for Kw depends on T, at 298 K Kw = 1014


T (K) 273
Kw

0.121014

298

313

373

1.01014

2.91014

5.41013

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b) pH
because of the wide range of concentrations of H+ commonly observed in
biological and chemical processes, a logarithmic scale is useful
pH = - log aH+
cannot measure for H+ in isolation, but we can estimate using the Debye-Hckel
equation. For a solution of 0.050 M HCl
+ = 0.509 2 = 0.509(1)2 0.050 = 0.114

+ = 0.77

= log(

)=

for dilute solutions at low ionic strength (i.e., [H+] 0.1 M and I 0.1 M), can
usually approximate with
pH = log[H+],
also,

i.e., 0.050 M HCl has a pH of 1.30

pOH = log[OH]
pH + pOH = 14

neutral solutions @ 25C: [H+] = [OH] = Kw = 1.010-14 = 107 M and pH = 7.00


acidic solutions @ 25C:

[H+] > [OH]

pH

basic solutions @ 25C:

[H+] < [OH]

pH

If we evaluate the pH of boiling water, Kw(100C) = 5.410-13


[H+] = Kw = 7.3510-7 and pH = 6.13 is neutral.

c) Dissociation of Acids and Bases


strong acids and bases are assumed to completely dissociate in water and
calculation of species concentrations is straight forward
weak acids and bases partially dissociate in water and calculations of species
concentrations is a little more complicated
for a weak acid HA
-

HA(aq) + H2O(l) A (aq) + H3O (aq)

Ka

a
(a )
(
)
=
H 3O +

( aHA ) ( aH O )
2

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the concentration of water in most solutions is close to that of pure water (i.e.,
1 L contains 55.5 mol) and so we can consider it in its standard state (i.e., pure
liquid) and approximate with aH 2O = 1
=
Ka

a )( a )
(=
H+

aHA

H + + A
[ HA] HA

since HA is an uncharged species, we can set HA 1 for dilute solutions and


substitute 2 for + H + A 2
Ka =
[ HA]

if the acid is sufficiently weak, the concentration of the ions are low ( 0.050 M)
and we can ignore 2 and write
H + A

Ka =
[ HA]
the magnitude of Ka indicates the degree of dissociation of the acid and thus the
acid strength (Refer to Table 8.1 Ka & pKa values for common weak acids at 298 K)

small Ka, ( little / much ) dissociation, ( stronger / weaker ) acid


large Ka, ( little / much ) dissociation, ( stronger / weaker ) acid
can also use the percent dissociation to indicate strength
H +
eq
percent dissociation
=
100%
[ HA]0

treatment of bases is similar, for NH3 the result is


Rxn: NH3(aq) + H2O(l) NH4+(aq) + OH-(aq)
NH 4 + OH
Kb =
NH 3

(Refer to Table 8.2 Kb & pKb values for common weak bases at 298 K)

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Example: Calculate the concentration of the undissociated acid, the H+ ions and the CN
ions of a 0.050 M HCN solution at 25C.

Rxn:
I
C
E

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d) Relationship between Ka and Kb


for a weak acid HA: HA(aq) + H2O(l) A(aq) + H3O+(aq)
A H +

Ka =
[ HA]

and for its conjugate base:

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

Kb =

[ HA] OH
A

If we were to add the two chemical equations together, i.e.,


HA(aq) + H2O(l) A(aq) + H3O+(aq); Ka
A(aq) + H2O(l) HA(aq) + OH(aq); Kb
H2O(l) + H2O(l) H3O+(aq) + OH(aq); K = ?
A H + [ HA] OH
K a Kb
=

[ HA]
A
= H + OH
= Kw

e) Salt Hydrolysis
ions that result from the dissociation of salts can undergo hydrolysis resulting in
acid or basic solutions
common examples are salts of weak acids or bases, e.g., sodium acetate forms a
basic solution; ammonium chloride forms an acidic solution
small, highly charged cations such as Be2+, Al3+ and Bi4+ can also hydrolyze
forming acidic solutions
e.g.,

AlCl3(s) Al3+(aq) + 3Cl(aq)

The Al3+ has a hydration sphere of six water molecules and the dense charge on
the cation polarizes the O-H bonds resulting in loss of a proton to the bulk water.
Al(H2O)63+(aq) + H2O(l) Al(H2O)5(OH)2+(aq) + H3O+(aq); Ka = 1.4105

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f) Polyprotic acids
more complicated than monoprotic
we will only consider biologically important carbonic acid and phosphoric acid

i) Carbonic acid
carbon dioxide on dissolving in water reacts to form carbonic acid, a diprotic
acid, i.e.,
CO2(aq) + H2O(l) H2CO3(aq)
the K for this reaction is small (0.00258) but experimentally we cant
distinguish between CO2(aq) and H2CO3(aq), so we generally treat them as the
single species H2CO3(aq)
the first dissociation constant is
H2CO3(aq) H+(aq) + HCO3(aq)
H + HCO3
K=
= 4.2 107
a1
H
CO
[ 2 3]

the conjugate base from the 1st dissociation becomes the acid for the 2nd
dissociation, i.e.,
HCO3(aq) H+(aq) + CO32(aq)

H + CO32
= 4.8 1011
K=
a2

HCO3
using these equations, we can calculate the concentration of the carbonate
species at any pH (refer to Example 8.2)
since K a 1 >> K a 2 we can make some generalizations
in a solution of carbonic acid, most of the H+
is generated by the 1st dissociation, and the 2nd
dissociation is negligible mathematically,
this results in the concentration of the
conjugate base from the 2nd dissociation is
numerically equal to K a2
no more than two of the carbonate species will
be present in significant concentrations at any
one pH
(Fig 8.1)
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ii) Phosphoric Acid


an important triprotic acid, i.e.,
H3PO4(aq) H+(aq) + H2PO4(aq)

K a1

H2PO4(aq)- H+(aq) + HPO42(aq)

K a2

HPO42-(aq) H+(aq) + PO43(aq)

K a3

we can use the same procedure used to calculate the concentrations of all the
species used above to calculate all four phosphate species

(Fig 8.2)

g) Buffers
are solutions containing a weak acid and its conjugate base or a weak base and its
conjugate acid at similar concentrations.
resist changes in pH on addition of small amounts of acid or base.
pH of bodily fluids varies greatly depending on location (blood plasma pH 7.4,
gastric juices pH 1.2) and maintaining these pHs is essential
enzymes will only work properly in a small range of pH values
pH balance also maintains the balance of osmotic pressure
equation generally used to determine the pH of a buffer is the
Henderson-Hasselbalch equation

=
pH pK a + log

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[conjugate base]
[conjugate acid ]

F14 CHEM 2880

the pH of the buffer depends on the pKa of the weak acid, and the relative amounts
of the two conjugates present
consider a buffer made from acetic acid and sodium acetate
the acid partially dissociates producing acetate and hydronium ions
CH3COOH(aq) + H2O(l) CH3COO(aq) + H3O+(aq)
the base partially hydrolyzes producing acetic acid
CH3COO(aq) + H2O(l) CH3COOH(aq) + OH(aq)
however, the presence of the acetate shifts the acid reaction to the left, and
the presence of the acetic acid shifts the base reaction to the left
essentially, no reaction occurs and we can consider the concentrations at
equilibrium to be the same as the initial concentrations.
on addition of a small amount of strong acid to this buffer, the acetate
would react with it producing acetic acid
on addition of a small amount of strong base, acetic acid would react with it
producing acetate
the base form of the H-H equation is
pOH
= pK b + log

[conjugate acid ]
[conjugate base]

i) Effect of Ionic Strength and Temperature on Buffers


a more rigorous treatment requires using activities
for a monoprotic acid HA, assuming the activity coefficient for HA is 1:

A
0.509 I
pH =
pKa + log
[ HA]
the addition of the last term can have significant effects on pH calculations,
especially in buffers where there is a significant ionic strength
most Ka values are measured at 25C, but most biological processes occur at 30
40C
Ka can be calculated at the higher temperature using the vant Hoff equation and
H and then the pH can be calculate using the H-H equation
Buffer Capacity - the amount of acid or base which must be added to a
buffer to produce a change in pH of one unit
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ii) Preparing buffers


weak acids buffer best within one pH unit of their pKa
to prepare a buffer of a specific pH
choose an appropriate acid/base pair (pKa pH)
use the H-H equation to calculate the ratio of base to acid
mix the acid and base together in this ratio
this is one of three ways to prepare a buffer:
mix conjugates together in approximately equal amounts
e.g., 1 CH3COOH + 1 CH3COONa
partially neutralize a weak acid by mixing weak acid and strong base in
approximately a 2:1 ratio
e.g., 2 CH3COOH + 1 NaOH
partially neutralize a weak base by mixing weak base and strong acid in
approximately a 2:1 ratio
e.g., 2 CH3COONa + 1HCl

h) Acid-Base Titrations
titration is an important analytical technique for determining concentrations of
solutions
acid/base titrations involving adding base from a buret to a solution of acid (or
vice versa) until the equivalence point is reached
the equivalence point can be detected by a number of methods, including using a
pH-meter and acid-base indicators
for titration of a strong acid with a strong base
the pH before the equivalence point is determined by the unreacted acid and is
usually strongly acidic
the pH at the equivalence point is _____
the pH after the equivalence point is determined by the excess base added and
is usually strongly basic

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for titration of a weak acid with a strong base


the pH before the equivalence point is determined by the unreacted acid and is
usually weakly acidic
the pH at the equivalence point is weakly ____________ due to the presence
of the conjugate base
the pH after the equivalence point is determined by the excess base added and
is usually strongly basic
for titration of a weak base with a strong acid
the pH before the equivalence point is determined by the unreacted base and is
usually weakly basic
the pH at the equivalence point is weakly ____________ due to the presence
of the conjugate acid
the pH after the equivalence point is determined by the excess acid added and
is usually strongly acidic

Fig 8.4

i) Acid-Base Indicators
weak acids and bases where the two conjugates are different colours.
colour changes when pH of soln is within one pH unit of the pKa of the indicator
pKIn 1
choose an indicator whose pKIn is close to the pH at the equivalence point
the point at which the indicator changes colour is the end point of the titration
ideally your end point should be at your equivalence point
Refer to Table 8.5 for some common acid-base indicators
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j) Amino Acids
behave as both acids and bases ampholytes
in solution exist as zwitterions +NH3CHRCOO
behaves as a base when titrated with hydrochloric acid
behaves as an acid when titrated with sodium hydroxide

Fig 8.5 - titration of glycine


pH at 1st half-equivalence point is pKa1
(or pKa)
pH at 2nd half-equivalence point is pKa2
(or pKa)
pH at first equivalence point where
zwitterion is predominate species is the
average of pKa1 and pKa2

k) Isoelectric Point (pI)


pH at which zwitterion does not move in an electric field net charge on molecule
is zero
determine which structure has a net zero charge, and average pKs on either side
to determine pI
e.g., Aspartic acid
pK a1 2.09
pK a2 3.86
=
=
+
+
3
2
3
2

NH CH(CH COOH)COOH
NH CH(CH COOH)COO

A: +1

B: 0

pK a3 =9.82

NH 3CH(CH 2COO- )COO-


NH 2CH(CH 2COO )COO

D: -2

C: -1

B is electrically neutral and the isoelectric point is

=
pI

2.09 + 3.86
= 2.98
2

pI values for amino acids are listed in Table 8.6


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k) Titration of proteins
proteins can be titrated to determine the number of dissociable protons

(Fig 8.7)
many equivalence points and much care must be taken for accurate assignments
can match pK values of these protons to those for amino acids to determine which
amino acid they came from
comparing these results to amino acid analysis of the protein can reveal
information on the structure of the protein
any dissociable protons not accounted for in the titration must be on groups
within the interior of the protein where they are not available for titration
these protons can be titrated if the protein is denatured.

l) Maintaining the pH of Blood


Reading assignment p. 293 - 297

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