Humboldt State University ® Department of Chemistry

Richard A. Paselk

 

General Chemistry

Spring 2009

Exercise: pH and Buffer Problems

© R. Paselk 2008
 
 

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pH and Buffer (Equilibrium) Problems

Answers


1. What is the pH of a solution of 0.033 M H2SO4?

First need to ask, is this a strong or a weak acid? Sulfuric acid, hydrochloric acid and nitric acid are the three common strong acids we use in the lab, and which we have memorized.

However, sulfuric acid is a strong acid for the first dissociation only. As a result the acid concentration is the hydrogen ion concentration, so [H+] = 0.033 M

And we know that pH = - log [H+]
pH = - log 0.033 = - (- 1.481)
pH = 1.48

Note that the significant figures are correct, 1 is the power of ten, only the figures to the right are significant.

 

2. What is the pH of a solution of 0.055 M barium hydroxide (it completely dissociates at this concentration).

First write out the formula for Barium hydroxide = Ba(OH)2

Note that the question states barium hydroxide is completely dissociated under these conditions, therefore it acts as a strong base.

As a result, [OH-] = 2 (0.055) = 0.11 M

To find pH however we need to know the hydrogen ion concentration, [H+]. Of course we know hydrogen ion concentration is related to hydroxide concentration by the relationship,

[H+][OH-] = 1.0 x 10-14

 

3. What is the pH of a 0.15 M solution of boric acid, H3BO3. Ka = 6.0 x 10-10

As we saw with sulfuric acid, only the first dissociation will occur when the acid is dissolved in water, so Ka is for the first dissociation only:

  H3BO3 right arrow H+ + H2BO3-
Before reaction 0.15 M   0 0
  0.15 M- x   x   x

Assume x << 0.15 since Ka is very small (6.0 x 10-10)

@ Equilibrium
H3BO3 = 0.15 M
  x   x
Ka = [H+][H2BO3-] / [H3BO3]

Substituting, Ka = (x)(x) / 0.15 = 6.0 x 10-10,

x2 = 9.0 x 10-11

x = 9.487 x 10-6 M; assumption OK.

pH = - log (9.487 x 10-6) = 5.023 = 5.02

Notice the significant figures. For a log function the number in front of the decimal is the exponent of ten,

thus pH = 5.02 is a 2 significant figure number!

 

4. Calculate the pH of a buffer made up by dissolving 0.150 moles sodium dihydrogenphosphate (NaH2PO4) and 0.100 moles of sodium hydrogenphosphate (Na2HPO4) in enough water to make 0.500 L of solution. Ka = 6.3 x 10-8 (FYI, this salt combination is commonly used in biological experiments, since it is a very effective buffer around pH 7.)

Note that sodium is a "spectator ion" and can be ignored in the buffer. Proceeding normally then, we first write the acid dissociation reaction for H2PO4-:

  H2PO4-  right arrow H+ + HPO4-2
Before reaction 0.150 moles/0.5L = 0.300M   0 0.100 moles/0.5L = 0.200M
@ Equilibrium
(0.300- x) M
assume x is small,
= 0.300M
  x  
(0.200 - x) M
assume x is small,
= 0.200M

Ka = [H+][HPO4-2] / [H2PO4-]

Substituting, Ka = (x)(0.200) / (0.300) = 6.3 x 10-8

Rearranging, [x] = (6.3 x 10-8)(0.300) / (0.200) = 9.45 x 10-8 ; assumption OK.

[H+] = 9.45 x 10-8

pH = 7.02

 

Alternatively we could use the Henderson-Hasselbalch equation, pH = pKa + log[A-] / [HA]:

First write the acid dissociation reaction too determine HA and A-:

HA right arrow H+ + A-

H2PO4- right arrow H+ + HPO4-2

 

Next find pKa = -log Ka= -log (6.3 x 10-8)

thus pKa = 7.20

substituting

pH = 7.20 + log (.200)/(.300) = 7.20 + (-0.1761)

pH = 7.02

 

5. Calculate the pH of a buffer made up by dissolving 0.0230 moles ascorbic acid (H2C6H6O6) and 0.0440 moles of sodium ascorbate (NaHC6H6O6) in enough water to make 0.250 L of solution. pKa = 4.30.

  H2C6H6O6  right arrow H+ + HC6H6O6-
Before reaction 0.0230 moles/0.25L = 0.0920M   0 0.0440 moles/0.25L = 0.176M
@ Equilibrium
(0.0920 - x) M
assume x is small,
= 0.0920M
  x  
(0.176 - x) M
assume x is small,
= 0.176M

Let HA = H2C6H6O6 and A-= HC6H6O6-

then, pH = pKa + log[A-] / [HA]

pH = 4.30 + log(0.176M)/(0.0920M) = 4.30 + (0.2817)

pH = 4.58

 

6. What ratio of sodium dihydrogenphosphate (NaH2PO4) and sodium hydrogenphosphate (Na2HPO4) will give a buffer with a pH = 7.00? pKa = 7.20

Easiest way to approach this is to use the Henderson-Hasselbalch equation to find the ratio of H2PO4- to HPO42-.

Let HA = H2PO4-and A-= HPO42-

then, pH = pKa + log[A-] / [HA]

Rearranging, log[A-] / [HA] = pH - pKa

Substituting, log[A-] / [HA] = 7.00 - 7.20 = -0.20

Now get rid of logs by raising both sides to power of ten: 10log[A-] / [HA] = 10-0.20

[A-] / [HA] = 0.631 = 0.63

[A-] = 0.63 [HA]

 

7. Calculate the pH of the solution resulting when 0.250 L of 0.500 M acetic acid is mixed with 0.250 L of 0.350 M sodium hydroxide. pKa = 4.74.

First we need to write out the reaction:

  CH2COOH  + OH- right arrow CH2COO-
Before reaction (0.25L)(0.5M)/0.5L = 0.250M   (0.25L)(0.35M)/0.5L = 0.175M 0
1:1 reaction, so hydroxide is limiting and will be completely consumed.
@ Equilibrium
0.250 - 0.175 = 0.0750M
  0  
0.175M

Easiest to use the Henderson-Hasselbalch equation to find the pH

pH = pKa + log[A-] / [HA] = pKa + log[CH2COO-] / [CH2COOH]

Substituting, pH = 4.74 + log(0.175/0.0750) = 4.74 + (0.3679) =5.108

pH = 5.11

Check: Compare the concentrations of the acid and conjugate base.

  • If the acid is in greater concentration, then the pH will be below the pKa
  • If the conjugate base is in greater concentration, then the pH will be higher than the pKa
  • In our example [A-] > [HA] and pH > pKa thus OK.

 


 


In addition to these exercises you should work on the text materials.


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© R A Paselk

Last modified 23 November 2009