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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
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
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,
pOH = log[OH]
pH + pOH = 14
pH
pH
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
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)
(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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Ka =
[ HA]
Kb =
[ HA] OH
A
[ 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.,
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
121
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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K a1
K a2
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 ]
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]
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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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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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
126
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
NH CH(CH COOH)COOH
NH CH(CH COOH)COO
A: +1
B: 0
pK a3 =9.82
D: -2
C: -1
=
pI
2.09 + 3.86
= 2.98
2
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.
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