Titration Acid Base

Chapter 12 Acid-Base Titrations
Strong Acid Strong Base Titrations Weak Acid Strong Base Weak Base Strong Acid
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Chem 253 - Chapter 12 - Acid/Base Titrations
Example titration of HCl with NaOH

Shape of the titration curve Conceptually this is very similar to the precipitation reaction curve we discussed in Chapter 7. Lets start with the MBE and CBE. CBE MBE [H+] + [Na+] = [Cl-] + [OH-] [Na+] = [OH-] [Cl-] = [H+]
10/10/2005 Chem 253 - Chapter 12 - Acid/Base Titrations 2
neglecting Kw.
Consider [Na+] and [Cl-] throughout Titration

It can be shown that MBE
[ Na + ] = Cb0Vb Va + Vb
&
[Cl ] =
0 Ca Va Va + Vb
where Va and Vb are the volumes of the acid and base solutions in the titration flask. C0a and C0b are the molarities of the acid and bases before addition.
Substituting back into the CBE
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CBE
[H + ] +
[H+] + [Na+] = [Cl-] + [OH-]

Cb0Vb C 0V = a a + [OH ] Va + Vb Va + Vb
Since we are interested in pH during titration solve for [H+]

[H + ] =
0 Ca Va C 0V b b + [OH ] Va + Vb Va + Vb
This our general relationship we will use in the following discussion.

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Before Equivalence Point

All of OH- consumed by excess H+
Now realize that before the equivalence point [OH-] 0
[H + ] =
Excess [H+]
0 Ca Va C 0V b b Va + Vb Va + Vb
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At the equivalence point

All of H+ is now consumed
At the equivalence point [OH-] = [H+]

0 Ca Va Cb0Vb = Va + Vb Va + Vb
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After the equivalence point

Excess OH[OH-] >> [H+] 0
[OH ] =
0 Cb Vb C 0V a a Va + Vb Va + Vb
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At any point on the titration curve, the fraction of H+ titrated () with HO- is
C b0Vb C b = 0 = mol titrant/mol analyte C a Va C a or Where Ca and Cb are the concentrations of acid and base in the titration mixture.
Cb =
C b0Vb Va + Vb
&
Ca =
0 Ca Va Va + Vb
When
< 1 before the equivalence point = 1 at the equivalence point > 1 after the equivalence point
Chem 253 - Chapter 12 - Acid/Base Titrations 8
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Example calculate the pH of the titration of 50.00 mL of 0.100 M HCl with 0.100 M NaOH
a) 40 mL of NaOH added The excess [H+] is
[H + ] =
0 Ca Va C 0V 0.100 M * 50.00mL 0.100 M * 40.00mL b b = Va + Vb Va + Vb 90.00mL
[H+] = 0.0111 M pH = 1.95 We can confirm this by calculating . = (0.100 M OH-*40.00 mL)/(0.100 M H+*50.00 mL) = 0.800
b) 50.00 mL of NaOH added

C b0Vb C b = 0 = C a Va C a
= (0.100 M OH-*50.00 mL)/(0.100 M H+*50.00 mL) = 1.00 We are at the equivalence point.
0 Ca Va C 0V = b b or simply [OH-] = [H+] Va + Vb Va + Vb
pH =7.000
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c) 60.00 mL of NaOH added

=
C b0Vb C b = 0 C a Va C a
= 0.100 M OH-*60.00 mL/0.100 M H+*50.00 mL = 1.2 We are after the equivalence point.
[OH ] = Cb0Vb C 0V 0.100 M * 60.00mL 0.100 M * 50.00mL a a = Va + Vb Va + Vb 110.00mL
[OH-] = 9.09e-3 pH = 11.96

Titration curve strong acid titrated with strong base

Note that only for the strong base strong acid case will the equivalence point pH be 7.00.
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Titration of a strong base (e.g. NaOH) with a strong acid (e.g. HCl) will appear as:
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Location of the equivalence point.

Acid-Base indicators respond to pH changes based on color changes. These indicators are all weak acids themselves. Phenolphthalein p 240. P2pink + 2H+ = H2P colorless pKa 8
The titration error occurs because the end point is pH 8 while the true equivalence point is pH 7.
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Remember when using visual indicators you must:

Use as little as possible since they are acids or bases and will react with your analyte. Pick the appropriate indicator. Based on expected equivalence point pH. See Table 124. We will skip a quantitative discussion of titration error.
Titration of a Weak Acid (HA) with a Strong Base (NaOH).

Similar considerations are at work here, well treat this case less rigorously. Consider the following example: 25.00 mL of 0.150 M CH3COOH (Ka = 1.75e5) is titrated with 0.200 M NaOH. Calculate the pH of the titration solution at
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a) 00.00 mL
The starting pH is simply, HA = 0.150 x H+ x + Ax
1.75e-5 = x2/0.150-x x = 1.62e-3 = [H+] pH = 2.793 this is the starting pH of this experiment.
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b) 10.00 mL
First we must consider the volume of the equivalence point to (Ve) know where we are on the titration curve: Ve = 25.00 mL* 0.150 M HA * 1/0.200 M NaOH = 18.75 mL @10.00 mL we are before the titration eq. point. Initial moles HA = 25.00 mL * 0.150 M HA = 3.75 mmol Added OH- = 10.00 mL * 0.200 M OH- = 2.00 mmol
HA + 3.75 mmol -2.00 mmol 1.75 mmol OH2.00 mmol -2.00 mmol 0 H2O + A+ 2.00 mmol 2.00 mol
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10
b) 10.00 mL continued
note that MBE is [HA] F = [HA] + [A-]
or in terms of amount (3.75 = 2.00 + 1.75) mmol 3.75 1.75 mmol = 2.00 mmol [HA] = 1.75 mmol/(35.00 mL) = 5.00e-2 M [A-] = 2.00 mmol/35.00 mL = 5.71e-2 M
b) 10.00 mL continued
Essentially what we have is a buffer system. Ka = 1.75e-5 = [H+][A-]/[HA] = [H+]5.71e-2/5.00e-2
[H+] = 1.53e-5 pH = 4.815

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c) 18.75 mL
The volume of the equivalence point to (Ve) is: Ve = 25.00 mL* 0.150 M HA * 1/0.200 M NaOH = 18.75 mL Note that HA molinitial = A- mol eq. pt.
= 25.00 mL* 0.150 M HA = 3.75 mmol HA or ATotal volume = 18.75 + 25.00 mL = 43.75 mL [A-] = 3.75 mmol/43.75 mL = 8.57e-2 M
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pH at equivalence point
All of HA is consumed left with A- which undergoes hydrolysis.
A+ 8.57e-2 -x H2O -= HA 0 +x + OH0 +x
Kb = Kw/Ka = 5.71e-10 = x2/[8.57e-2 x] x = 7.00e-6 M pOH = 5.155 pH = 8.845 note that it is not 7.00.
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d) 25.00 mL
We are past the end point so we should expect a region in which we have excess OH-.
Mol excess OH- = mol OH- added initial mol HA 25.00 mL * 0.200 M NaOH = 5.00 mmol OHMol excess OH- = 5.00 mmol 3.75 mmol = 1.25 mmol [OH-] = 1.25 mmol / 50.00 mL = 2.50e-2 M pOH = 1.602 pH = 12.398
Fig 12-2
APredominates
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HA Predominates
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13
Role of Ka and [HA]initial Figure 12-3

This makes the titration of low concentrations and/or high pKa acids difficult.
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Titration of a weak base with a strong acid.
Consider the titration of NH3 with HCl. Rxn: NH3 + HCl NH4+ + Cl-
Example 50.00 mL of 0.222 M NH3 (Ka NH4+ = 5.5e-10) is titrated with 0.155 M HCl.
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a) 0.00 mL
NH3 + 0.222 -x H2O = -NH4+ + 0 +x OH0 +x
Kb = 1.00e-14 / 5.5e-10 = x2 / 0.222-x x = [OH-] = 2.01e-3 M pH = 11.30

b) 50.00 mL 0.155 M HCl added

First calculate volume of equivalence point: Ve Ve = 50.00 mL * 0.222 M NH3 * 1/0.155 M = 71.61 mL HCl solution We can see that we are before the end point, i.e. excess NH3. Initial mol NH3 = 50.00 mL * 0.222 M = 11.1 mmol Added mol HCl = 50.00 mL * 0.155 M = 7.75 mmol Note that = mol a/ mol b = 7.75/11.1 = 0.698
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pH at 50.00 mL 0.155 M HCl added

Excess NH3 = 11.1 7.75 mmol = 3.35 mmol [NH3] = 3.35 mmol / 100.00 mL = 3.35e-2 M must calculate [NH4+] NH3 11.1 -7.75 + HCl 7.75 -7.75 NH4+ 0 +7.75 + Cl0 +7.75
mol NH4+ = 7.75 mmol [NH4+] = 7.75 mmol / 100.00 mL = 7.75e-2 M
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This a pH region where both NH3 and NH4+ are present

Ka = [H+][NH3] / [NH4+] 5.5e-10 = [H+] 3.35e-2 M / 7.75e-2 M [H+] = 1.27e-9 pH = 8.90
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pH = pKa at Ve added
What happens at 35.805 mL ( 71.61 mL) of 0.155 M HCl added? Initial mol NH3 = 50.00 mL * 0.222 M = 11.1 mmol Added mol HCl = 35.805 mL * 0.155 M = 5.55 mmol Mol NH3 left = 11.1 5.55 mmol = 5.55 mmol Ka = [H+][NH3] / [NH4+] = [H+] 5.55mmol / 5.55 mmol pKa = pH = 9.26 (vol. of solution cancel)
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c) pH at the equivalence point, Ve, 71.61 mL of 0.155 M HCl added

[NH3+] = 11.1 mmol / 121.61 mL = 9.13e-2 M or = 1 Here all of NH3 is consumed and we are left with:
NH4+ 9.12e-2M -x = NH3 0 +x + H+ 0 +x
5.5e-10 = x2 / 9.12e-2 x x = 7.08e-6 M pH = 5.15

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d) 80.00 mL of 0.155 M HCl.

Initial mol NH3 = 11.1 mmol Added mol H+ = 80.00 mL * 0.155 M = 12.4 mmol = 12.4/11.1 = 1.12 Excess H+ = 12.4 11.1 mmol = 1.3 mmol [H+] = 1.3 mmol / 130.00 mL = 0.010 M pH = 2.00
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Summary of titration of 50.00 mL of 0.222 M NH3 with 0.155 M HCl.

a) b) c) d) Vol of HCl added 0.00 mL 35.81 mL 50.00 mL 71.61 mL 80.00 mL pH 11.30 9.26 8.90 5.15 2.00
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Titration of Weak Base with Strong Acid

12 10 8 pH 6 4 2 0 0 50 Vol. Hcl Added
Series1
Buffer region Excess HCl
100
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Diprotic systems.
In cases where the polyprotic acid has well separated pKa vaules, each step can be treated individually. Example Consider the titration of 50.00 mL of 0.050 M H2CO3 (Ka1 = 4.5e-7, Ka2 = 5.6e-11) with 0.100 M NaOH.
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a) 0.00 mL
The solution consists only of 0.050 M H2CO3. H2CO3 0.050 M -x = H+ 0 +x + HCO30 +x
4.5e-7 = x2 / 0.050 x x = 1.5e-4 pH = 3.82

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b) 10.00 mL 0.100 M NaOH solution

Calculate the mol OH- added and initial moles of H2CO3. Initial mol H2CO3 = 50.00 mL * 0.050 M = 2.5 mmol Added mol OH- = 10.00 mL * 0.100 M = 1.00 mmol Excess mol H2CO3 = 2.5 1.00 mmol = 1.5 mmol [H2CO3] = 1.5 mmol / 60.00 mL = 2.5e-2 M Must realize that this is a buffer system (why?).
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Realizing that this is a buffer system we must calculate [HCO3-]

From an MBE consideration: initial mol H2CO3 = mol H2CO3 left + mol HCO3- formed 2.5 mmol = mol H2CO3 + mol HCO3- = 1.5 + x x = 1.0 mmol [HCO3-] = 1.0 mmol / 60.00 mL = 1.67e-2 Ka1 = 4.5e-7 = [H+][HCO3-] / [H2CO3] 4.5e-7 = [H+]1.67e-2 / 2.5e-2 [H+] = 6.75e-7 pH = 6.17 note that volumes of solution cancel
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c) 25.00 ml added
Initial mol H2CO3 = 50.00 mL * 0.050 M = 2.5 mmol Added mol OH- = 25.00 mL * 0.100 M = 2.5 mmol This is the first equivalence point. [HCO3-] = 2.5 mmol / 75.00 mL = 0.033 M HCO3- = CO32- + H+ & H+ + HCO3- = H2CO3
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[H + ]
K a1 K a 2 F + K a1 K w K a1 + F
4.7 10 7 (5.6 10 11 )0.033 + 4.7 10 710 14 [H ] 4.7 10 7 + 0.033

+
[H+] = 5.04e-9 pH = 8.30 also

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pH = (pK1 + pK2) = 8.29

d) 28.00 mL
We should recognize that that we will have HCO3- and CO32-, which constitutes a buffer system. Initial mols HCO3- = 2.5 mmol Mols OH- beyond 1st eq. pt. = (28.00 25.00) mL * 0.100 M = 0.30 mmol mols HCO3- = 2.5 0.3 mmol = 2.2 mmol [HCO3-] = 2.2 mmol / 78.00 mL = 2.82e-2 M
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MBE
2.5 mmol = [HCO3-] + [CO32-] = 2.2 + x
x = 0.30 mmol [CO32-] = 0.3 / 78.00 mL = 3.85e-3 Ka2 = 5.6e-11 = [H+][CO32-] / [HCO3-] = [H+]*3.85e-3 / 2.82e-2 [H+] = 4.10e-10 pH = 9.39
e) 50.00 mL 0.100 M NaOH added

Initial mol H2CO3 = 50.00 mL * 0.050 M = 2.5 mmol Added mol OH- = 50.00 mL * 0.100 M = 5.0 mmol This is the second eq. pt. Sole species [CO32-] = 2.5 mmol / 100.00 mL = 0.025 M CO320.025 M -x + H2O -= HCO3- + 0 +x OH0 +x
Kb = 1.00e-14 / 5.6e-11 = x2 / 0.025 x x = 2.11e-3

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pH = 11.32
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f) 53.00 mL of 0.100 M NaOH

We are 3.00 mL beyond the 2nd eq. pt. Excess [OH-] = 3.00 mL * 0.100 M = 0.300 mmol [OH-] = 0.300 mmol / 103.00 mL = 2.91e-3 M pH = 11.464
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Summary
Vol titrant 0.00mL 10.00 25.00 28.00 50.00 53.00 pH 3.82 6.17 8.30* 9.39 11.32* 11.464 excess H2CO3 1st buffer region 2nd buffer region excess OH-
Draw entire curve.

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Read about the case of a weak base with a strong base in section 12-4 p232 of your text. Read about how to locate the equivalence point with a pH electrode in section 12-5 of your text.
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Location of end points by 1st and 2nd derivatives
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25
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Titration Acid Base

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Titration Acid Base

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Chapter 12 Acid-Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

Example titration of HCl with NaOH

Consider [Na+] and [Cl-] throughout Titration

Substituting back into the CBE

Chem 253 - Chapter 12 - Acid/Base Titrations

[H+] + [Na+] = [Cl-] + [OH-]

Since we are interested in pH during titration solve for [H+]

This our general relationship we will use in the following discussion.

Before Equivalence Point

Chem 253 - Chapter 12 - Acid/Base Titrations

At the equivalence point

At the equivalence point [OH-] = [H+]

Chem 253 - Chapter 12 - Acid/Base Titrations

After the equivalence point

Chem 253 - Chapter 12 - Acid/Base Titrations

b) 50.00 mL of NaOH added

c) 60.00 mL of NaOH added

[OH-] = 9.09e-3 pH = 11.96

Titration curve strong acid titrated with strong base

Chem 253 - Chapter 12 - Acid/Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

Location of the equivalence point.

Chem 253 - Chapter 12 - Acid/Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

Remember when using visual indicators you must:

Titration of a Weak Acid (HA) with a Strong Base (NaOH).

Chem 253 - Chapter 12 - Acid/Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

[H+] = 1.53e-5 pH = 4.815

Chem 253 - Chapter 12 - Acid/Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

Role of Ka and [HA]initial Figure 12-3

Chem 253 - Chapter 12 - Acid/Base Titrations

Titration of a weak base with a strong acid.

Kb = 1.00e-14 / 5.5e-10 = x2 / 0.222-x x = [OH-] = 2.01e-3 M pH = 11.30

b) 50.00 mL 0.155 M HCl added

pH at 50.00 mL 0.155 M HCl added

mol NH4+ = 7.75 mmol [NH4+] = 7.75 mmol / 100.00 mL = 7.75e-2 M

Chem 253 - Chapter 12 - Acid/Base Titrations

This a pH region where both NH3 and NH4+ are present

Chem 253 - Chapter 12 - Acid/Base Titrations

c) pH at the equivalence point, Ve, 71.61 mL of 0.155 M HCl added

5.5e-10 = x2 / 9.12e-2 x x = 7.08e-6 M pH = 5.15

d) 80.00 mL of 0.155 M HCl.

Summary of titration of 50.00 mL of 0.222 M NH3 with 0.155 M HCl.

Chem 253 - Chapter 12 - Acid/Base Titrations

Titration of Weak Base with Strong Acid

Chem 253 - Chapter 12 - Acid/Base Titrations

4.5e-7 = x2 / 0.050 x x = 1.5e-4 pH = 3.82

b) 10.00 mL 0.100 M NaOH solution

Realizing that this is a buffer system we must calculate [HCO3-]

Chem 253 - Chapter 12 - Acid/Base Titrations

Chem 253 - Chapter 12 - Acid/Base Titrations

4.7 10 7 (5.6 10 11 )0.033 + 4.7 10 710 14 [H ] 4.7 10 7 + 0.033

[H+] = 5.04e-9 pH = 8.30 also

pH = (pK1 + pK2) = 8.29

2.5 mmol = [HCO3-] + [CO32-] = 2.2 + x

e) 50.00 mL 0.100 M NaOH added

Kb = 1.00e-14 / 5.6e-11 = x2 / 0.025 x x = 2.11e-3

f) 53.00 mL of 0.100 M NaOH

Draw entire curve.

Chem 253 - Chapter 12 - Acid/Base Titrations