5: PH Measurement and Its Applications (Experiment) - Chemistry LibreTexts
5: PH Measurement and Its Applications (Experiment) - Chemistry LibreTexts
HIn(aq) + H2 O(l) −
⇀
↽− In− (aq) + H3 O+ (aq) (5.1)
⏟yellow ⏟ blue
In this hypothetical example In stands for the indicator. As you can see from Equation 5.1 , the protonated form of the acid-base
indicator, HIn (aq), will be one color (yellow in this example) and the deprotonated form, In− (aq), will be another color (blue in
this example). The equilibrium-constant expression for Equation 5.1 is:
[H3 O+ ][In− ]
Kai = (5.2)
[HIn]
This equation can also be written as:
[In− ] Kai
= (5.3)
[HIn] [H 3 O + ]
Generally only one or two drops of indicator are added to the solution of interest and therefore the amount of H3 O+ due to the
indicator itself can be considered negligible. The total amount of H3 O+ in the solution is therefore controlled by the
concentrations of the other acids and/or bases present in the solution. Note that when [H3 O+ ] >> Kai , [HIn] >> [In– ] (the
equilibrium will be shifted to the left in accord with Le Chatelier's principle) and the color of the solution will be essentially the
same as color I. Similarly, when [H3 O+ ] << Kai , [HIn] << [In– ] (the equilibrium will be shifted to the right) and the color of
the solution will be essentially the same as color II.
As an example consider an acidic solution containing the indicator HIn where [H3 O+ ] >> Kai , and therefore, [HIn] >> [In– ]
. Under these conditions the solution will be yellow. Suppose we add base to the solution resulting in a decrease of [H3 O+ ]. As
[H3 O+ ] decreases the equilibrium indicated by Equation 5.1 will shift to the right and [HIn] will decrease while [In– ]
increases. When [In– ] becomes significant compared to [HIn] the color of the solution will begin to change. Eventually as
[H3 O+ ] decreases still further we will have, [H3 O+ ] << Kai , and the color of the solution will have turned to blue. In other
words the solution will change color when [HIn] ≈ [In– ] , and so Kai = [H3 O+ ] , or pKai = pH . In general we can say that an
acid-base indicator changes color at a pH determined by the value of Kai or pKai for that particular indicator.
The five indicators you will use in this experiment, their color transitions, and their respective values of pKai are given in Table 1.
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The actual colors in solution vary somewhat from those shown here depending on the concentration. *Thymol blue is a
polyprotic acid with two pKa values. The second pKa is around 8.8. Adding too much NaOH, to a pH beyond its second pKa
results in a colorless solution.
We can use the values in Table 1 to determine the approximate pH of a solution. For example, suppose we have a solution in
which methyl violet is violet. This tells us that the pH of our unknown solution is greater than or equal to 2 because methyl
violet turns violet at pH values of 2 or greater. Now suppose we add some congo red to a fresh sample of our solution and find
that the color is violet. This tells us that the pH of our solution is less than or equal to 3 because congo red turns violet at pH
values of 3 or less. From these two tests we know that the pH range our solution is between 2 and 3. Thus, we have determined
the pH of our solution to within one pH unit. Proceeding in a similar manner, you will use the acid-base indicators in Table 1 to
determine the pH range of four solutions to within one pH unit.
Part C: Using pH to Determine the Value of Ka for Acetic acid, CH3 COOH (aq)
In this part of the experiment you will use your pH meter to measure the pH of two acetic acid solutions of known
concentration. From the measured pH and concentration of a weak acid solution you can determine the value of Ka for the acid.
The general equation for the dissociation of a weak acid, HA (aq), in water is:
HA(aq) + H2 O(l) −
⇀
↽− A(aq) + H3 O+ (aq) (5.4)
For which
[A][H3 O+ ]
Ka = (5.5)
[HA]
When we construct an ICE table for this reaction we can see that at equilibrium
[H3 O+ ]2
Ka = (5.8)
[HA]0 − [H3 O+ ]
+
[ ]
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Because [H3 O+ ] can be determined by measuring the pH of the weak acid and [HA]0 is known you can determine the value of
Ka using Equation 5.8 .
Part D: Determining the Value of Ka for an Unknown Acid by Titration
Note: There are two procedures listed for this part. Please consult your instructor to see which procedure is appropriate for
your lab section.
1. Titration is performed without collecting pH data for a Titration curve.
2. OPTIONAL procedure: Titration is performed while collecting pH data for a Titration curve.
For either procedure you will perform a titration on an unknown acid. You may assume that this acid is a weak monoprotic acid.
You will divide the solution containing this unknown acid into two equal parts. One part you will set aside and the other part
will be titrated with NaOH . Upon completion of the titration, the titrated solution will contain only the conjugate base of the
weak acid according to
log[A− ]
pH = pKa + (5.10)
[HA]
Because [HA] = [A− ] , the pH of this buffer solution equals the value of pKa for the unknown acid. Thus we can use the
measured pH of this buffer solution to determine the value of pKa for our unknown acid.
OPTIONAL
If time allows you will measure the pH as a function of the volume of NaOH solution added in the titration. These data will be
used to plot a titration curve for your unknown acid. You will then use this curve to find the midpoint of the titration. At the
midpoint of the titration of a weak acid with a strong base, pH = pKa . Thus we can use the midpoint of the titration curve to
confirm the value of pKa for the unknown acid.
Procedure
Materials and Equipment
Equipment:
You will need the following additional items for this experiment: pH meter, magnetic stirrer and stir-bar, 50-mL buret
Safety
Students must wear safety goggles and lab coats at all times.
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sodium carbonate
sodium bisulfate
methyl yellow
congo red
bromocresol green
phenolphthalein
unknown acid
WASTE DISPOSAL: All chemicals used must go in the proper waste container for disposal.
Part C: Using pH to Determine the Value of Ka for Acetic Acid, CH3 COOH (aq)
1. Rinse two small 100 or 150-mL beakers as before. Put 30 mL of 1.0 M acetic acid solution into the first beaker and 30 mL of
0.010 M acetic acid solution into the second.
2. Use your pH meter to determine the pH of each solution. Record the results on your data sheet. You will use these values to
calculate Ka .
**Consult your instructor before starting Part D, to see if he/she wants you to follow the normal or OPTIONAL procedure.
Part D: Determining the Value of Ka for an Unknown Acid by Titration (Normal procedure)
1. Obtain a 50-mL buret from the stockroom. A buret stand should be available in the laboratory room. Rinse your buret, small
funnel, and four 150-mL beakers several times using deionized water.
2. Select one of the 150-mL beakers and label it “NaOH”. Rinse this beaker once more with about 5 mL of 0.2 M NaOH . Then
use it to collect about 75 mL of the 0.2 M NaOH solution (available in the reagent fume hood).
3. Rinse the 50-mL buret and funnel once with about 5 mL of 0.2 M NaOH solution. Clamp the buret to the buret stand
making sure that it is vertical. Insert your funnel into the top of the buret.
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4. Fill the buret with the 0.2 M NaOH solution from your beaker to just above the 0.00-mL mark. Remove the funnel. Using a
waste beaker allow the NaOH solution to flow from the buret tip dropwise until the bottom of the meniscus of the NaOH
solution in the buret is exactly at the 0.00-mL mark when read at eye level. If you miss this mark, add some additional 0.2 M
NaOH from your beaker and try again.
5. Obtain a vial containing your unknown solid acid from your instructor and record the letter and number of this unknown
acid on your data sheet.
6. Weighing by difference measure between 1.5 and 2.0 grams of the unknown acid into one of the clean rinsed 150-mL beakers.
Record this mass on your data sheet. Label this beaker, “A- ”.
7. Using your large graduated cylinder, measure out exactly 100.0 mL of deionized water. Combine this with the unknown
solid acid sample in your 150-mL beaker. Stir your solution to completely dissolve the solid acid.
8. Using your large graduated cylinder, measure out 50.0 mL of your unknown acid solution and transfer this to a second 150-
mL beaker. Label this second beaker “HA” and set it aside for now.
9. Add 2 drops of phenolphthalein indicator to the remaining 50.0-mL of unknown acid solution in the beaker labeled “A- ”.
10. Titrate the solution in the beaker labeled “A- ”. until it reaches the phenolphthalein end point. The end point is near when the
pink color from the phenolphthalein indicator begins to persist in solution longer before vanishing. When you notice these
changes slow down your addition rate to just 2 to 3 drops per addition. When you feel you are nearing the endpoint, slow
down your addition rate to just 1 drop per addition. When the pink color from the phenolphthalein indicator persists for at
least 2 minutes you have reached the endpoint of your titration.
11. We now need to equalize the volumes in the two beakers labeled “HA” and “A- ”. Using your large graduated cylinder
measure a volume of deionized water equal to the total amount of the 0.2 M NaOH you added during your titration and add
this volume of deionized water to the contents of the beaker labeled, “HA”. Swirl gently to mix.
12. Using your large graduated cylinder measure out 25-mL of the solution from the beaker labeled “HA” and transfer this
volume to your fourth clean rinsed 150-mL beaker. Label this beaker, “50-50 buffer mixture.”
13. Now measure out 25-mL of the solution from the beaker labeled “A- ” and combine this with the solution in your beaker
labeled “50-50 buffer mixture”. Swirl gently to mix. Using your pH meter, measure the pH of this solution and record the
value on your data sheet.
14. The pH of the solution in your beaker labeled, “50-50 buffer mixture,” is also the pKa of your unknown acid. Do you know
why? You will need to tell your instructor this value for Part E.
15. Save the remaining solutions in the beakers labeled, “HA” and“A- ” and the beaker containing the remaining 0.2 M NaOH
solution for the next part of this experiment.
Part D: Determining the Value of Ka for an Unknown Acid by Titration (OPTIONAL procedure)
Follow the procedure below for Part D instead of the steps above if your instructor wants you to also obtain a pH titration
curve
1. Obtain a magnetic stirrer, magnetic stir-bar, and 50-mL buret from the stockroom. A buret stand should be available in the
laboratory room.
2. Rinse your buret, small funnel, and four 150-mL beakers several times using deionized water.
3. Select one of the 150-mL beakers and label it “NaOH”. Rinse this beaker once more with about 5 mL of 0.2 M NaOH . Then
use it to collect about 75 mL of the 0.2 M NaOH solution.
4. Rinse the 50-mL buret and funnel once with about 5 mL of 0.2 M NaOH solution. Clamp the buret to the buret stand
making sure that it is vertical. Insert your funnel into the top of the buret.
5. Fill the buret with the 0.2 M NaOH solution from your beaker to just above the 0.00-mL mark. Remove the funnel. Using a
waste beaker allow the NaOH solution to flow from the buret tip dropwise until the bottom of the meniscus of the NaOH
solution in the buret is exactly at the 0.00-mL mark when read at eye level. If you miss this mark, add some additional 0.2 M
NaOH from your beaker and try again.
6. Obtain a vial containing your unknown solid acid from your instructor and record the letter and number of this unknown
acid on your data sheet.
7. Weighing by difference measure between 1.5 and 2.0 grams of the unknown acid into one of the clean rinsed 150-mL beakers.
Record this mass on your data sheet. Label this beaker, “A- ”.
8. Using your large graduated cylinder, measure out exactly 100.0 mL of deionized water. Combine this with the unknown
solid acid sample in your 150-mL beaker. Stir your solution to completely dissolve the solid acid.
9. Using your large graduated cylinder, measure out 50.0 mL of your unknown acid solution and transfer this to a second 150-
mL beaker. Label this second beaker “HA” and set it aside for now.
-
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10. Add 2 drops of phenolphthalein indicator to the remaining 50.0-mL of unknown acid solution in the beaker labeled “A- ”.
11. Put the magnetic stirrer onto your buret stand so that the buret is directly over the magnetic stirrer.
12. Place the magnetic stir-bar into the solution in the beaker labeled “A- ”. and set this beaker on top of the magnetic stirrer.
Plug in the magnetic stirrer and set it to the lowest setting where the solution is mixing smoothly but gently. If the magnetic
stirrer also has a heater function be certain that this remains off throughout this experiment.
13. Using a ring stand and your utility clamp, or the stand and clamp provided with your pH meter’s probe, set up the pH meter
so that the probe is supported inside the swirling solution in your beaker, low enough down that the meter can read the pH,
but high enough up so that the probe tip does not contact the rotating magnetic stir-bar, as shown in Figure 1. Set the probe
off to one side of the beaker so that liquid from the buret can directly enter the beaker during the titration.
Figure1
14. Use the pH meter to measure the pH of the solution in the beaker labeled “A- ”. Record this value in the table on your data
sheet. This pH is the “initial point” in your titration.
15. Dispense approximately 0.5-mL of the 0.2 M NaOH solution from your buret into your beaker. Reading the buret carefully,
record the exact volume added on your data sheet. Use the pH meter to measure the pH of the solution following this
addition. Record this value in your data table alongside the measured volume.
16. Proceeding in this way, continue to add 0.2 M NaOH to your solution in approximately 0.5-mL steps. Continue recording
the total volume added and the measured pH following each addition on your data sheet.
17. Observe the pH change after each addition carefully. At some point during your titration the pH difference between
subsequent 0.5-mL additions will start to grow larger. Around this time, the pink color from the phenolphthalein indicator
will also begin to persist in solution longer before vanishing. When you notice these changes slow down your addition rate to
just 2 to 3 drops per addition. When the pH again begins to jump and you feel you are nearing the endpoint, slow down your
addition rate to just 1 drop per addition. Continue to record the volume added and the pH after each addition.
18. When the pink color from the phenolphthalein indicator persists for at least 2 minutes you have reached the endpoint of your
titration. Note this point on your data sheet and stop the titration. In this experiment it is OK if you overshoot this mark by a
few drops. (If you overshoot the endpoint by more than this you may need to repeat this titration, see your instructor for how
to proceed).
19. We now need to equalize the volumes in the two beakers labeled “HA” and “A- ”. Using your large graduated cylinder
measure a volume of deionized water equal to the total amount of the 0.2 M NaOH you added during your titration and add
this volume of deionized water to the contents of the beaker labeled, “HA”. Swirl gently to mix.
20. Using your large graduated cylinder measure out 25-mL of the solution from the beaker labeled “HA” and transfer this
volume to your fourth clean rinsed 150-mL beaker. Label this beaker, “50-50 buffer mixture.”
21. Now measure out 25-mL of the solution from the beaker labeled “A- ” and combine this with the solution in your beaker
labeled “50-50 buffer mixture”. Swirl gently to mix. Using your pH meter, measure the pH of this solution and record the
value on your data sheet.
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22. The pH of the solution in your beaker labeled, “50-50 buffer mixture,” is also the pKa of your unknown acid. Do you know
why? You will need to tell your instructor this value for Part E.
23. Save the remaining solutions in the beakers labeled, “HA” and “A–” and the beaker containing the remaining 0.2 M NaOH
solution for the next part of this experiment.
Indicator used 0.1 M HCl 0.1 M NaH 2 PO4 0.1 M CH3 COOH 0.1 M ZnSO4
Methyl violet
Thymol blue
Methyl yellow
Congo Red
Bromcresol green
pH range
Consider your results for the solutions of 0.1 M HCl and 0.1 M CH3 COOH . Which has the lower pH and why is its pH
lower?
Consider your results for the 0.1 M ZnSO4 solution. Is the solution acidic or basic? ____________
Which ion, Zn2 + or SO24 − , is causing the observed acidity or basicity? ____________
Write the net ionic equation below that shows why this ion is acidic or basic:
0.1 M NaCl 0.1 M Na2 CO3 0.1 M CH3 COONa 0.1 M NaHSO 4
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Measured pH
Color in indicator
Consider your results for the 0.1 MNaCl solution. Is the color obtained when tested with bromcresol green indicator as
expected? Explain.
Consider your results for the 0.1 M Na2 CO3 solution. Is the solution acidic or basic?____________
Which ion, Na+ or CO23 − is causing the observed acidity or basicity?____________
Write the net ionic equation below that shows why this ion is acidic or basic:
Consider your results for the 0.1 M NaHSO 4 solution. Is the solution acidic or basic?____________
Which ion, Na+ or HSO− 4
is causing the observed acidicity or basicity?____________
Write the net ionic equation below that shows why this ion is acidic or basic:
Write the chemical equation describing the equilibrium reaction between acetic acid and water:
Part C – Using pH to Determine the Value of Ka for Acetic Acid, CH3 COOH (aq)
Complete the following table. Use the known value of Ka for acetic acid from your textbook to determine the percentage error
in your measured Ka value for each solution.
Measured pH
[H3 O+ ]equil
[CH3 COO–− ]equil
[CH3 COOH]equil
Ka (calculated)
Ka (textbook)
Percent error
Show your calculations (using an equilibrium or ICE table) for obtaining the value of Ka for the 0.010 M solution (only):
0.00 mL (initial
1 26
point)
2 27
3 28
4 29
5 30
6 31
7 32
8 33
9 34
10 35
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11 36
12 37
13 38
14 39
15 40
16 41
17 42
18 43
19 44
20 45
21 46
22 47
23 48
24 49
25 50
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pH change
Briefly explain why the buffer is more resistant to a change of pH upon addition of the base than the water. Use equations to
support your explanation:
Why isn’t the measured pH of the deionized water before adding the NaOH (aq) equal to 7.0?
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