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WeakAcidBaseNotes PDF
WeakAcidBaseNotes PDF
163
Notice that....
[H2O] (constant at . 55.6 M) does not appear in Ka or Kb.
The larger the Ka the stronger the acid; the larger the Kb the
stronger the base.
EXAMPLE:
CCR3COOH;
CH3COOH;
Ka = 2.0 x 101
Ka = 1.8 x 10-5
CH3NH2;
NH3;
Kb = 6.4 x 10-4
Kb = 1.8 x 10-5
Hs on C are not (generally) acidic in water e.g. CH3COOH monoprotic (one H+) and one Ka
pKb = - log Kb
EXAMPLES:
pKa for CCR3COOH = 0.70
pKa for CH3COOH = 4.74
The weaker the acid or base, the larger the pKa or pKb..........
164
H+
CH3COO
165
So...
General Guideline:
This assumption; a negligible amount of the acid being ionized - is
acceptable if x # 5% of the initial concentration of acid......
This will generally be the case if the concentration of the acid, c,
divided by the Ka value is > 100.
EXAMPLE:
166
Equil. [H+]
2.6 x 102
7.9 x 103
2.3 x 103
decreasing
% Dissoc.
2.6
7.9
22
increasing
167
pH
1.59
2.10
2.64
increasing
Strategy
Always write the reaction for the weak acid given in the question.
Write the equilibrium constant expression for the reaction.
Identify what you know and what you are asked to find.
Usually, its a fairly straightforward matter of substituting for the
appropriate variables in the Equilibrium Constant Expression.
Sometimes there are a few intermediate calculations to perform....
168
EXAMPLE 1:
Nitrous acid, HNO2 has a Ka value of 6.0 x 10 4.
Calculate the initial concentration of HNO2 if a solution of this acid
has a pH of 3.65.
169
EXAMPLE 2:
A 0.025 M solution of formic acid, HCOOH, has a pH of 2.75.
a) Calculate the % ionization of this solution.
b) Calculate the Ka for formic acid.
170
The most commonly used weak bases are Ammonia (NH3) and its
derivatives.
In these compounds one (or more) N atom has a pair of electrons
not used (yet !) for bonding (a lone pair).
EXAMPLES:
: NH3 +
CH3NH2
H2O
H2O
NH4+ +
CH3NH3+
OH
+
OH
171
EXAMPLE 1:
What is the % ionization and pH of a solution of a 0.085 M solution of
NH3 ? [Kb = 1.8 x 10 5]
172
EXAMPLE 2:
A solution of methylamine, CH3NH2, has a pH of 10.45. Calculate the
initial concentration of methylamine in this solution.
[Kb of CH3NH2 = 6.4 x 10 4]
173
EXAMPLE 3:
Calculate the Kb for the weak base B, if a 0.00365 M solution of that
base is 8.50 % ionized.
174
Every weak acid (HA), will produce its conjugate base (A) when it
ionizes in water.
The conjugate base of any acid is the species that is obtained from
the acid by removal of one H+ (or proton).
Every weak base (B), will produce its conjugate acid (BH+) when it
ionizes in water.
175
EXAMPLES:
Consider the weak acid HNO2; its conjugate base is NO2.
Now look at the weak base NH3 ; its conjugate acid is NH4+.
Or...to get the same result, we could add the equations, and then (as
we have seen earlier in these notes; p. 137) their Ks are multiplied:
176
EXAMPLE 1:
HF, a weak acid: Ka = 7.24 x 10 4;
F , (conjugate base of HF)
pKb =
pKa = 3.14
Kb =
EXAMPLE 2:
CH3COOH, a weak acid: Ka = 1.8 x 10 5; pKa = 4.74
CH3COO , (conjugate base of CH3COOH)
pKb =
Kb =
EXAMPLE 3:
HCN, a very weak acid: Ka = 4.00 x 10 10; pKa = 9.40
CN , (conjugate base of HCN)
pKb =
Kb =
177
Now look at the generic weak base B, whose conjugate acid is BH+.
BH+ will act like an acid.......
As was the case with the weak acids, the weaker the base, the
more acidic is its conjugate acid.
EXAMPLE 1:
NH3 is a weak base; Kb = 1.8 x 105; pKb = 4.74
NH4+ (conjugate acid of NH3); pKa =
Ka (NH4+) =
EXAMPLE 2:
Aniline, C6H5NH2, is a very weak base; Kb = 4.0 x 1010; pKb = 9.40
C6H5NH3+ (conjugate acid of C6H5NH2) ; pKa =
Ka =
178
Salts
You may have noticed that the conjugate base of a weak acid, or the
conjugate acid of a weak base is always an ion.
So where does this ion come from?
It is always produced when the parent weak acid or base ionizes,
but these conjugate species can be also be found in ionic
compounds.
And ions are formed when an ionic solid is dissolved in water........
Remember those solubility rules ????
This is where they come in handy; so you will know whether or not a
solid will dissolve in water to produce ions!!
First we consider salts that yield the conjugate base of a weak acid.
Recall that the conjugate base will always behave like a base when
in aqueous solution:
BH + + OH
B + H2 O
EXAMPLE 1:
Consider the salt CH3COONa.
In water........
179
EXAMPLE 2:
Calculate the pH and % hydrolysis ( % base ionization) in 0.100 M KF .
[Ka for HF = 7.24 x 10 4]
180
EXAMPLE 2:
A 0.0285M solution of the sodium salt, NaA of the weak monoprotic
acid, HA, has a pH of 9.65. Calculate Ka for the acid, HA.
181
Salts that produce the conjugate acids of weak bases will exhibit
acidic behaviour in solution................
HA
H2O
H3 O +
EXAMPLE 1:
The salt in question is NH4CR. In water:
EXAMPLE 2:
In water:
Then.....
182
NaOH
strong
NaCR +
H2O
neutral
If both ions which form the salt (NaCR in this case) originally came
from strong species, they may termed spectator ions and the
solution will be neutral.
In contrast:
CH3COOH + NaOH !
weak
strong
CH3COONa+ + H2O
basic solution
183
HCR
+
strong
NH3
weak
NH4+CR + H2O
acidic solution
NH4+CR
H2O
185
EXAMPLE 1:
Calculate the pH at the equivalence point of the titration of 25.00 mL
of 0.165 M benzoic acid, C6H5COOH, with 0.185 M KOH.
[Ka for C6H5COOH = 6.6 x 105]
186
EXAMPLE 2:
Calculate the pH at the equivalence point of the titration of 0.175 M
methylamine, CH3NH2, with 0.250 M HNO3.
[Kb for CH3NH2 = 6.4 x 104 ]
187
In
At 1 pH unit below this pKa value (acidic) the indicator is 90% in the
HIn form.
At 1 pH unit above this pKa value (basic) the indicator is 90% in the
In form.
The approximate range for colour change: 2 pH units.
Selection of Indicator
The indicator must change colour near the equivalence point.
For a strong acid/strong base titration: the pKa of the indicator
should be 5 -9 , although in practice the pH changes so rapidly at
the end-point that any indicator is suitable.
For a weak acid/strong base titration: the pKa of the indicator must
be in the basic region, for example: phenolphthalein, pKa . 9
For a strong acid/weak base titration: the pKa of the indicator must
be in the acidic region, for example: methyl orange, pKa . 3.4
188
H+
CH3COO
CH3COOH
H+
189
CH3COO
EXAMPLE 1:
190
EXAMPLE 2:
In a solution [NaOH] = 0.020 M and [NH3] = 0.15 M. (Kb = 1.8 x 105)
What is the % ionization of the NH3? What is the pH of this solution ?
191
Polyprotic acids are those which have more than one acidic
hydrogen.
This means that they dissociate (or ionize) in stages, with Ka values
for each step.
H2CO3 H+ + HCO3
K1 = 4.2 x 107
Step 2:
HCO3 H+ + CO32
K2 = 4.8 x 1011
Overall:
H2CO3 2 H+ + CO32
Koverall = K1 x K2
192
EXAMPLE:
Consider the acid dissociation of 0.25 M H2CO3.
What are the concentrations of all species in the equilibrium mixture,
the % dissociation in each stage, and the pH?
[ K1 = 4.2 x 10!7, K2 = 4.8 x 1011]
First acid dissociation:
193
General Result:
[A2] = K2
194
HCO3 + H2O
H2CO3 + OH
(base)
OR:
HCO3
H+ !
+ OH
H2CO3
! H2O + CO3 2
195
BUFFER SOLUTIONS
Lets start with looking at buffers which contain a weak acid and its
conjugate base.
196
197
EXAMPLE 2:
What is the pH of the previous solution if it was diluted to a volume of
10.0 L?
198
EXAMPLE 3:
What mass, in grams, of NaNO2 must be added to 700 mL of 0.165 M
HNO2 to produce a solution with a pH of 3.50 ?
[Ka(HNO2) = 6.0 x 10 4]
199
But buffer solutions are not only made from weak acids..................
Lets look at a buffer solution made from a weak base and its
conjugate acid:
EXAMPLE 1:
A solution was prepared by adding 21.5 g of NH4CR to 1.50 L of 0.25 M
NH3(aq). Calculate the pH of this solution. [Kb for NH3 = 1.8 x 10 5]
200
EXAMPLE 2:
What mass of CH3NH3CR must be added to 650 mL of a 0.145 M
solution of CH3NH2 to produce a solution with pH = 10.50 ?
[Kb of CH3NH2 = 6.4 x 10 4]
201
EXAMPLE 1:
100 mL of 0.50 M Benzoic Acid, C6H5COOH, is mixed with 100 mL of
0.20 M NaOH. What is the pH of the resulting solution ?
[Ka of C6H5COOH = 6.6 x 10 5]
202
EXAMPLE 2:
Calculate the pH of a solution prepared by mixing 150 mL of 0.140 M
ammonium chloride, NH4CR, with 100 mL of 0.112 M KOH.
[Kb for NH3 = 1.8 x 10 5]
203
EXAMPLE 1:
200 mL of a 0.180 M solution of methylamine, CH3NH2, are mixed with
150 mL of a 0.125 M solution of HCRO4. What is the pH of this
solution?
204
EXAMPLE 1:
0.20 mol of formic acid, HCOOH, and 0.15 mol of sodium formate,
HCOONa, are made up to 1.0 L volume, to give a solution having
pH = 3.60. What happens to the pH if we add 0.03 mol of HCR to this
solution ?
[Ka of HCOOH = 1.9 x 10 4]
205
206
EXAMPLE 3:
What change in pH would occur if we added the same amounts of HCR
(as in Ex. 1) and NaOH (as in Ex. 2) to 1.0 L of just water (instead of
buffer) ?
207
EXAMPLE 2:
A solution contains 0.60 mol of NH4CR and 0.30 mol of NH3(aq) in 1.5 L.
The pH of the solution is 8.95. What will be the change in pH if we add
0.07 mol of HCR to this solution ?
208
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