This is a quick and accurate method for determining acidic or basic substances in many samples.

Several inorganic acids and bases. Hundreds of organic species. The titrant is typically a strong acid or base. The sample species can be either a strong or weak acid or base.

COOH COO- K+

COOH

As a last resort, you can standardize an HCl solution with a standard NaOH solution. Standardization verses a secondary standard is not recommended in most cases. Each standardization introduces an error so your results are less reliable if NaOH is used.

While chemical indicators can be used for endpoint detection, a pH electrode is the best way to monitor an acid base titration.

Plot of ml titrant (or % titration) vs pH will result in a typical titration curve.

pH

% titration

mmoles acid - mmoles base total volume

mmoles excess total volume

ml titrant 0 10 20 30 40 50 60 70 80 90

total ml 100 110 120 130 140 150 160 170 180 190

[H3O+] 0.10 0.082 0.067 0.054 0.043 0.033 0.025 0.018 0.011 0.0053

pH 1.00 1.09 1.17 1.28 1.37 1.48 1.60 1.74 1.96 2.28

(100 ml)(0.10 M) - (10 ml)(0.10 M) 100 ml + 10 ml

2.5 2

pH

1.5 1 0.5 0

30

60

90

ml NaOH

7 6 5

pH

4 3 2 1 0 0 10 20 30 40 50 60 70 80 90 100

10 ml 210 ml

ml NaOH

ml titrant total V

[OH-]

pH

14 12 10

110 120 130 140 150 160 170 180 190 200

210 220 230 240 250 260 270 280 290 300

0.0048 0.0091 0.013 0.017 0.020 0.023 0.026 0.029 0.031 0.033

11.68 11.96 12.11 12.23 12.30 12.36 12.41 12.46 12.49 12.52

pH

8 6 4 2 0
100 120 140 160 180 200 20 40 60 80 0

ml NaOH

basic sample

pH acidic sample

ml titrant

The concentration of either our sample or titrant can affect the shape of our titration curve.
different acid sample concentrations

We get a similar effect as the concentration of the titrant is reduced. This is one of the reasons that most strong acid-base titrations are done in the 0.5-0.1 M range.

As the [acid] decreases, we get a less distinct jump in pH.

First, well only be concerned about the titration of a weak acid with a strong base or a weak base with a strong acid. !We still have the same four general regions for our titration curve. !The calculation will require that you use the appropriate KA or KB relationship. acid base !Well start by reviewing the type of calculations involved and then work through an example.

[H3O+][A-] [HA]

[OH-][HA] [A-]

[A-] [HA] [HA] [A-]

% titration 100 - % titration

[H3O+][A-] [HA]

x2 0.10

% titration 100 - % titration

% titration 0 10 20 30 40 50 60 70 80 90

pH 2.60 3.24 3.60 3.83 4.02 4.20 4.38 4.57 4.80 5.15

Note: At 50% titration, pH = pKA Also, the was only a change of 1.91 pH units as we went from 10 to 90 % titration. pH

5 4 3 2 1 0 0 20 40 60 80 100

% titration

[OH-][HA] [A-]

9 8

x2 0.050
pH

7 6 5 4 3 2 1 0 0 20 40 60 % titration 80 100

ml titrant 110 120 130 140 150

total volume 210 220 230 240 250

[OH-] 0.0048 0.0091 0.013 0.017 0.020

pH 11.68 11.96 12.11 12.23 12.30

This is identical to what we obtained for our strong acid/strong base example

14 12 10

pH

8 6 4 2 0 0 50 100 150

% titration

During an acid-base titration, the indicator acts as an additional weak acid or base. pH It must be weaker than the species being determined - titrated after analyte. It must be present at relatively low concentrations so as not to interfere with the normal titration curve and equivalence point. It must give a sharp and distinct color change. % titration eq. pt.

Normal titration curve pH Too much indicator is present

% titration

1 10 10 1

Indicator Bromophenol Blue Methyl Orange Methyl Red Bromothymol Blue Cresol Purple Phenolphthalein Thymolphthaleine Alizerin Yellow GG

pH transition range 6.2 - 7.6 3.1 - 4.4 4.2 - 6.2 6.2 - 7.6 7.6 - 9.2 8.3 10 9.3 - 10.5 10 12

color yellow - blue red - orange red - yellow yellow - blue yellow - purple colorless - red colorless - blue yellow - red

Phenophthalein

Methyl Red

Bromothymol blue

[A-] [HA]

Initially, each solution is at pH 7.00. After adding 10 ml of 1.0 M HCl we have: Pure water (10 ml)(1.0 M) [H3O+] = (110 ml) pH = 1.04

= 0.091

This is a pretty big jump!

Addition of 10 ml 1.0 M HCl to our buffered system. We started with 0.10 moles of both the acid and conjugate base forms. The addition of our first 10 ml can be expected to react the the conjugate base, converting it to the acid. After addition, there are 0.09 moles of the base form and 0.11 moles of the acid form.
[A-] [HA] 0.09 mmol 1.1 mmol

ml HCl added 0 10 20 30 40 50 60 70 80 90

pH unbuffered 7.00 1.04 0.78 0.64 0.54 0.48 0.43 0.39 0.35 0.32

buffered 7.00 6.91 6.82 6.73 6.63 6.52 6.40 6.25 6.05 5.72

6 5

pH

4 3 2 1 0 0 20 40

buffered unbuffered

60

80

100

ml HCl added

For the addition of 100 ml of HCl, we have converted virtually all of A- to HA so the calculation is different. KA = 1.00 x 10-7 = [H+][A-] [HA]

When we account for dilution, 1.0 M = [HA] + [A-] where [A ] is negligible. This is a standard weak acid calculation.

7 6 5

Obviously, a buffer only has a limit ability to reduce pH changes. buffered unbuffered The pKA determines the range where a buffer is useful. The concentration of our buffer system determines how much acid or base it can deal with.

pH

4 3 2 1 0 0 20 40

60

80

100

ml HCl added

[A-] [HA] [A-] [HA]

Assume that [ HA ] = [ A- ] = C, where C is the initial concentration of either the acid or base Buffer capacity in general is then 1 = log [ A- ]
[A-] [HA] Well only worry about addition of a base.

= 10 [ HA ]

Concentration, M 1.0 0.50 0.10 0.050 0.010

Buffer capacity (mol) 0.22 0.11 0.022 0.011 0.0022

[A-]

= 2 C - [ HA ]

[ HA ] = 0.22 C

The capacity may be smaller if you dont start with a 1:1 mixture.