ENVE 102 ENVIRONMENTAL CHEMISTRY

2019-2020 SPRING SEMESTER

RECITATION #10

Question 1. Which acid-conjugate base pair, and what ratio of acid to conjugate base
should be used to buffer different solutions at pH.

a. 7.0
b. 2.0

State your reasons and sources of information clearly.

Question 2. A buffer is prepared to contain 0.005 M ammonia (NH3) and 0.02 M NH4Cl
(Ka = 5.62*10-10).

a. Find the pH of the buffer

b. Is this buffer system a good buffer if we like to keep the pH at 9.2?
c. Is this buffer system a good buffer if we like to keep the pH at 7.5?
d. Find the pH of the buffer after addition of NaOH to yield a final concentration of
0.005 M
e. Find the pH of the buffer after addition of HCl into the original buffer to yield a final
concentration of 0.0025 M

Note: Volume changes with addition of NaOH or HCl can be neglected, you can directly
use the concentrations given in question.

Question 3. Acetic acid and sodium acetate will be used to prepare a buffer solution to
stabilize the pH at 5.0. Ka of acetic acid is 10-4.7.

a. Find the salt/acid ratio required.

b. Will this be an effective buffer?

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 ENVE 102 ENVIRONMENTAL CHEMISTRY
2019-2020 SPRING SEMESTER
RECITATION #10
ANSWER KEY

Question 1. Which acid-conjugate base pair, and what ratio of acid to conjugate base
should be used to buffer different solutions at pH.

a. 7.0
b. 2.0

State your reasons and sources of information clearly.

Answer 1

The pH values that the solutions has to be maintained at are given as 7.0 and 2.

a. Desired pH = 7.0

pKa of an acid will fall in the middle of the well-buffered zone. So, an acid with a pKa value
close to 7 has to be found. If such an acid and its conjugate base is added to the solution,
the addition of some volume of acid or base will not change the pH of the solution
drastically (i.e. maintain it around pH 7.0).

Check Table 4.1 from Snoeyink & Jenkins (2001, pp.90-91) to see the pKa values of
different species. Look for species with pH values close to 7.0.

Hydrogen sulfide
𝐻2 𝑆 + 𝐻2 𝑂 ↔ 𝐻𝑆 − + 𝐻3 𝑂+ pKa = 7.1

Dihydrogen phosphate
𝐻2 𝑃𝑂4 − + 𝐻2 𝑂 ↔ 𝐻𝑃𝑂4 2− + 𝐻3 𝑂+ pKa = 7.2

It can be said that either one of hydrogen sulfide or dihydrogen phosphate could be used
by only considering their pKa values. However, an environmental engineer should be
more cautious. Hydrogen sulfide is actually not desirable due to:

 Being toxic
 Having foul odor (similar to rotten eggs)
 Being very volatile (hard to keep it dissolved in the solution)

So, dihydrogen phosphate is selected.

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To find the required ratio of acid-conjugate base couple we use Handerson - Hasselbach
Eqn:
𝐶
𝑝𝐻 = 𝑝𝐾𝑎 + log ( 𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒 )
𝐶 𝑎𝑐𝑖𝑑

Substituting:
𝐶
7.0 = 7.2 + log ( 𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒 )
𝐶 𝑎𝑐𝑖𝑑

𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒
log ( ) = 0.2
𝐶𝑎𝑐𝑖𝑑
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒
= 10−0.2 = 0.6310
𝐶𝑎𝑐𝑖𝑑

The question asks for an acid to conj. base ratio, so reciprocate:

𝐶𝑎𝑐𝑖𝑑 1
= = 1.585
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒 0.6310

b. Desired pH = 2.0

Same procedure as above. Check Table 4.1 from Snoeyink & Jenkins (2001, pp.90-91) to
see the pKa values of different species. Look for species with pH values close to 2.0.

Bisulfate ion
𝐻𝑆𝑂4 − + 𝐻2 𝑂 ↔ 𝑆𝑂4 2− + 𝐻3 𝑂+ pKa = 2.0

No other alternatives are necessary. Use Handersan-Hasselbah Eqn. to find the ratio of
conjugate base to acid.
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒
2.0 = 2.0 + log ( )
𝐶𝑎𝑐𝑖𝑑
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒
log ( )=0
𝐶𝑎𝑐𝑖𝑑
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠𝑒
= 100 = 1
𝐶𝑎𝑐𝑖𝑑

Reciprocate:
𝐶𝑐𝑜𝑛𝑗.𝑏𝑎𝑠 1
=1=1
𝐶𝑎𝑐𝑖𝑑

Question 2. A buffer is prepared to contain 0.005 M ammonia (NH3) and 0.02 M NH4Cl
(Ka = 5.62*10-10).

a. Find the pH of the buffer

b. Is this buffer system a good buffer if we like to keep the pH at 9.2?
c. Is this buffer system a good buffer if we like to keep the pH at 7.5?
d. Find the pH of the buffer after addition of NaOH to yield a final concentration of
0.005 M
e. Find the pH of the buffer after addition of HCl into the original buffer to yield a final
concentration of 0.0025 M

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Note: Volume changes with addition of NaOH or HCl can be neglected, you can directly
use the concentrations given in question.

Answer 2

a. Find the pH of the buffer

𝑝𝐾𝑎 = − log(5.62 ∗ 10−10 ) = 9.250

Use Handerson-Hasselbach Eqn:

𝐶𝑏𝑎𝑠𝑒
𝑝𝐻 = 𝑝𝐾𝑎 + log (𝐶 )
𝑐𝑜𝑛𝑗.𝑎𝑐𝑖𝑑

Substituting:
0.005
𝑝𝐻 = 9.250 + log ( 0.02 )
𝑝𝐻 = 8.648

b. Is this buffer system a good buffer if we like to keep the pH at 9.2?

The most effective range of a pH buffer is for desired pH values within the range pKa±1.5.

9.250-1.5 ≤ Desired pH range ≤ 9.250+1.5

7.750≤ Desired pH range ≤ 10.750

9.2 is in this range, so it is a good system for this purpose.

c. Is this buffer system a good buffer if we like to keep the pH at 7.5?

7.5 is not in the range calculated above, so it is not a good system for this purpose.

d. Find the pH of the buffer after addition of 0.005 M NaOH

This is the addition of a strong base.

𝑁𝑎𝑂𝐻 → 𝑁𝑎+ + 𝑂𝐻 − (0.005 M)

Ignoring volume changes, add this amount (0.005 M) to the amount of base already
present and subtract it from the conjugate acid already present. Then, substitute those
into Handerson-Hasselbach Eqn:

0.005+0.005 0.01
𝑝𝐻 = 9.250 + log ( 0.02−0.005 ) = 9.250 + log (0.015) = 9.074

e. Find the pH of the buffer after addition of 0.0025 M HCl to the original buffer

This is the addition of a strong acid.

𝐻𝐶𝑙 + 𝐻2 𝑂 → 𝐶𝑙 − + 𝐻3 𝑂+ (0.0025 M)

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Ignoring volume changes, add this amount (0.0025 M) to the amount of conjugate acid
already present and subtract it from the base already present. Then, substitute those into
Handerson-Hasselbach Eqn:

0.005−0.0025 0.0025
𝑝𝐻 = 9.250 + log ( 0.02+0.0025 ) = 9.250 + log (0.0225) = 8.296

CAUTION: Be careful that in this question, the final concentrations of the added acid or
base is given, with the overall volume the same for all. If, for example, volume (mL) of acid
or base added is given, then the change in total volume of buffer may need to be calculated.

Question 3. Acetic acid and sodium acetate will be used to prepare a buffer solution to
stabilize the pH at 5.0. Ka of acetic acid is 10-4.7.

a. Find the salt/acid ratio required.

b. Will this be an effective buffer?

Answer 3

The solution is similar to Question 2.

a. Find the salt/acid ratio required.

𝑝𝐾𝑎 = − log(10−4.7 ) = 4.7

Use Handerson-Hasselbach Eqn:

𝐶
𝑝𝐻 = 𝑝𝐾𝑎 + log ( 𝑐𝑜𝑛𝑗,𝑏𝑎𝑠𝑒 )
𝐶 𝑎𝑐𝑖𝑑

Substituting:
𝐶
5.0 = 4.7 + log ( 𝑐𝑜𝑛𝑗,𝑏𝑎𝑠𝑒 )
𝐶 𝑎𝑐𝑖𝑑
𝐶𝑐𝑜𝑛𝑗,𝑏𝑎𝑠𝑒
log ( ) = 0.3
𝐶𝑎𝑐𝑖𝑑
𝐶𝑐𝑜𝑛𝑗,𝑏𝑎𝑠𝑒
= 100.3 = 1.995
𝐶𝑎𝑐𝑖𝑑

What is meant by salt (sodium acetate) is actually the conjugate base of acetic acid. So the
solution is 1.995.

b. Will this be an effective buffer?

The most effective range of a pH buffer is for desired pH values within the range pKa±1.5.

4.7-1.5 ≤ Desired pH range ≤ 4.7+1.5

3.2 ≤ Desired pH range ≤ 6.2

5.0 is in this range, so acetic acid-sodium acetate couple is an effective buffer.