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Example 15.

Identify the conjugate acid-base pairs in the reaction between


ammonia and hydrofluoric acid in aqueous solution
NH3(aq) + HF(aq) NH+4 (aq) + F-(aq)

Example 15.1
Strategy

Remember that a conjugate base always has one fewer H atom


and one more negative charge (or one fewer positive charge)
than the formula of the corresponding acid.
Solution
NH3 has one fewer H atom and one fewer positive charge than
NH+4 . F- has one fewer H atom and one more negative charge
+
than HF. Therefore, the conjugate acid-base pairs are (1) NH4
and NH3 and (2) HF and F-.
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Example 15.2

The concentration of OH- ions in a certain household ammonia


cleaning solution is 0.0025 M. Calculate the concentration of
H+ ions.

Example 15.2

Strategy
We are given the concentration of the OH- ions and asked to
calculate [H+]. The relationship between [H+] and [OH-] in water
or an aqueous solution is given by the ion-product of water, Kw
[Equation (15.3)].

Example 15.2
Solution
Rearranging Equation (15.3), we write
-14
K
1.0

10
-12
w
[H + ] =
=
=
4.0

10
M
0.0025
[OH ]

Check

Because [H+] < [OH-], the solution is basic, as we would expect


from the earlier discussion of the reaction of ammonia with
water.
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Example 15.3

The concentration of H+ ions in a bottle of table wine was


3.2 x 10-4 M right after the cork was removed. Only half of the
wine was consumed. The other half, after it had been
standing open to the air for a month, was found to have a
hydrogen ion concentration equal to 1.0 x 10-3 M. Calculate the
pH of the wine on these two occasions.

Example 15.3

Strategy
We are given the H+ ion concentration and asked to calculate
the pH of the solution. What is the definition of pH?

Example 15.3
Solution
According to Equation (15.4), pH = -log [H+]. When the bottle
was first opened, [H+] = 3.2 x 10-4 M, which we substitute in
Equation (15.4)

pH = -log [H+]
= -log (3.2 x 10-4) = 3.49
On the second occasion, [H+] = 1.0 x 10-3 M, so that
pH = -log (1.0 x 10-3 ) = 3.00
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Example 15.3

Comment
The increase in hydrogen ion concentration (or decrease in pH)
is largely the result of the conversion of some of the alcohol
(ethanol) to acetic acid, a reaction that takes place in the
presence of molecular oxygen.

Example 15.4

The pH of rainwater collected in a certain region of the


northeastern United States on a particular day was 4.82.
Calculate the H+ ion concentration of the rainwater.

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Example 15.4
Strategy

Here we are given the pH of a solution and asked to calculate


[H+]. Because pH is defined as pH = -log [H+], we can solve for
[H+] by taking the antilog of the pH; that is, [H+] = 10-pH, as
shown in Equation (15.5).

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Example 15.4
Solution
From Equation (15.4)
pH = -log [H+] = 4.82

Therefore,
log [H+] = -4.82
To calculate [H+], we need to take the antilog of -4.82
[H+] = 10-4.82 = 1.5 x 10-5 M
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Example 15.4

Check
Because the pH is between 4 and 5, we can expect [H+] to be
between 1 x 10-4 M and 1 x 10-5 M. Therefore, the answer is
reasonable.

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Example 15.5

In a NaOH solution [OH-] is 2.9 x 10-4 M. Calculate the pH of the


solution.

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Example 15.5
Strategy
Solving this problem takes two steps. First, we need to
calculate pOH using Equation (15.7). Next, we use Equation
(15.9) to calculate the pH of the solution.

Solution
We use Equation (15.7):

pOH = -log [OH-]


= -log (2.9 x 10-4)
= 3.54
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Example 15.5
Now we use Equation (15.9):
pH + pOH = 14.00
pH = 14.00 - pOH
= 14.00 - 3.54 = 10.46

Alternatively, we can use the ion-product constant of water,


Kw = [H+][OH-] to calculate [H+], and then we can calculate the
pH from the [H+]. Try it.
Check The answer shows that the solution is basic (pH > 7),
which is consistent with a NaOH solution.
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Example 15.6

Calculate the pH of a
(a) 1.0 x 10-3 M HCl solution

(b) 0.020 M Ba(OH)2 solution

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Example 15.6
Strategy
Keep in mind that HCl is a strong acid and Ba(OH)2 is a strong
base. Thus, these species are completely ionized and no HCl
or Ba(OH)2 will be left in solution.

Solution
(a)The ionization of HCl is
HCl(aq)

H+(aq) + Cl-(aq)

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Example 15.6
The concentrations of all the species (HCl, H+, and Cl-) before
and after ionization can be represented as follows:

Initial (M):
Change (M):
Final (M):

H+(aq)

+ Cl-(aq)

1.0 x 10-3
-1.0 x 10-3

0.0
+1.0 x 10-3

0.0
+1.0 x 10-3

0.0

1.0 x 10-3

1.0 x 10-3

HCl(aq)

A positive (+) change represents an increase and a negative


(-) change indicates a decrease in concentration. Thus,
[H+] = 1.0 x 10-3 M
pH = -log (1.0 x 10-3)
= 3.00

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Example 15.6
(b) Ba(OH)2 is a strong base; each Ba(OH)2 unit produces two
OH- ions:

Ba(OH)2(aq)

Ba2+(aq) + 2OH-(aq)

The changes in the concentrations of all the species can


be represented as follows:
Ba(OH)2(aq)

Initial (M):
Change (M):
Final (M):

0.020
- 0.020
0.00

Ba2+(aq)

+ 2OH-(aq)

0.00
+ 0.020
0.020

0.00
+2(0.020)
0.040
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Example 15.6
Thus,
[OH-] = 0.040 M
pOH = -log 0.040 = 1.40
Therefore, from Equation (15.8),

pH = 14.00 - pOH
= 14.00 - 1.40
= 12.60
Check Note that in both (a) and (b) we have neglected the
contribution of the autoionization of water to [H+] and [OH-]
because 1.0 x 10-7 M is so small compared with 1.0 x 10-3 M
and 0.040 M.
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Example 15.7

Predict the direction of the following reaction in aqueous


solution:
HNO2(aq) + CN-(aq)

HCN(aq) + NO-2 (aq)

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Example 15.7
Strategy

The problem is to determine whether, at equilibrium, the


reaction will be shifted to the right, favoring HCN and NO-2, or to
the left, favoring HNO2 and CN-. Which of the two is a stronger
acid and hence a stronger proton donor: HNO2 or HCN? Which
of the two is a stronger base and hence a stronger proton
acceptor: CN- or NO-2 ? Remember that the stronger the acid,
the weaker its conjugate base.

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Example 15.7

Solution
In Table 15.2 we see that HNO2 is a stronger acid than HCN.
Thus, CN- is a stronger base than NO-2 . The net reaction will
proceed from left to right as written because HNO2 is a better
proton donor than HCN (and CN- is a better proton acceptor
than NO-2 ).

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