Volumetric Methods

(i) Acid-Base Titrations

Definition

Acid base titration is the same as neutralization titration in which we have:

𝐻+ + O𝐻 → 𝐻2O

- Note that the range in pH change of reaction depends on the concentration of the acid

and indicator.

Consider the reaction between 𝑯+ and 𝑶𝑯 - to give 𝑯𝟐𝑶

2𝐻2𝑂 ⇌ 𝐻3𝑂+ + O𝐻− or H2O ⇌ H+ + OH-

[𝐻+][𝑂𝐻−]
𝐾𝑒𝑞u𝑖𝑙 =
𝐻2𝑂

𝐾𝑤 = [𝐻+][𝑂𝐻−] − − − −(2)

𝑊ℎ𝑒𝑟𝑒: 𝐾𝑤 = 𝑖𝑜𝑛 𝑝𝑟𝑜𝑑𝑢𝑐𝑡 𝑐𝑜𝑛𝑠𝑎𝑛𝑡 𝑜𝑓 𝑤𝑎𝑡𝑒𝑟 = 1.0 𝑥 10−14

By definition:

𝑝𝐻 = − log[𝐻+]

𝐼𝑛𝑡𝑟𝑜𝑑𝑢𝑐𝑒 − log 𝑖𝑛 𝑒𝑞𝑛 2.

− log 𝐾𝑤 = − log[𝐻+] + − log[𝑂𝐻−]

Therefore p𝐾𝑤 = 𝑝𝐻 + 𝑝𝑂𝐻

𝑝𝐾𝑤 = −𝑙𝑜𝑔𝐾𝑤 = −𝑙𝑜𝑔1.0 𝑥 10−14 = 14 = 𝑝𝐻 + 𝑝𝑂𝐻

𝑖. 𝑒. − log 𝐾𝑤 = 𝑝𝐾𝑤 = 14

INDICATOR FOR ACID BASE TITRATION

Theory of Indicator behaviour

Acid base indicators are fairly high molecular weight weak organic acids or bases, which

upon dissociation or association undergo structural changes that give rise to alterations in
color. The indicator is usually added to the solution and visually detect as a color change.

The color of the ionized form of the indicator is usually different from the non-ionized

form. One form may be colorless, but the other form may be colored.

SYMBOLIC REPRESENTATION OF TYPICAL REACTION OF ACID BASE

INDICATOR

Suppose we have an indicator of a weak acid, designated Hln, and assume that the non-

ionized form is red while the ionized form is blue thus:

(a) H2O + Hln ⇌ H3O+ + ln-

Acid color (red) Basic color (blue)

(b) ln- + H2O ⇌ lnH+ + OH-

Basic color acid color

( Base indicator)

At equilibrium concentrations for each reaction can be calculated thus:

[𝐻3𝑂+][ ln−]
𝑘𝑎= [𝐻ln]
- -------------(3)

[ln𝐻+][𝑂𝐻−]
𝑘𝑏= [ln]
----------- (4)

Rearranging equations 3 & 4

[ ln− ] 𝑘 - ----- (5)

=
[𝐻𝑙𝑛] [𝐻3𝑂+]

[ ln𝐻+] 𝑘𝑏 - ------------------- (6)

=
[ 𝑙𝑛] [𝑂𝐻−]

But 𝑘𝑤 = [𝑂𝐻−][𝐻3𝑂+]
𝑘𝑤
[𝑂𝐻−] = substitute this is equation 6
[𝐻3𝑂+]

[ ln𝐻+] 𝑘𝑏 𝑘𝑏[𝐻3𝑂+]
= =
[ 𝑙𝑛] 𝑘𝑤 𝑘𝑤
[𝐻3𝑂+]

𝐵𝑢𝑡 𝑘𝑏 and 𝑘𝑤 𝑎𝑟𝑒 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

 [ ln𝐻+]
Hence = [𝐻 𝑂+]
[ 𝑙𝑛] 3

[ ln𝐻+]
Hence as [𝐻 𝑂+] change there will be a change in concentration of ratio
3 [ 𝑙𝑛]
Similarly, again recall that 𝑘𝑤 = [𝑂𝐻−][𝐻3𝑂+]

Therefore [𝐻3𝑂+] = 𝑘𝑤/𝑂𝐻−

Substitute this in equation 5 and solve as before you will get:

[ ln−]
= [OH-]
[𝐻𝑙𝑛]

[ ln−]
Hence a change in [OH-] will result in change of ratio
[𝐻𝑙𝑛]

With indicator in which both forms are colored, generally only one color is observed if

the ratio of the concentration of the two forms is 10:1; only the color of the more

concentrated form is seen. When only the color of the non-ionized form is seen, then

[ ln−]
= 1/10
[𝐻𝑙𝑛]
[ ln−] 1
Hence for ≤ acid color predominate
[𝐻𝑙𝑛] 10

[1𝑛−] 10
For ≤ Base color predominate
[𝐻1𝑛] 1

To evaluate the range of [𝐻+] concentration needed to effect the color change of

indicator we have:

[𝐻3𝑂+][ ln−]
from equation 3 ------ 𝑘𝑎= [𝐻ln]

1
𝑘 = [𝐻 𝑂+]
𝑎 3
10

[𝐻3𝑂+] = 10𝑘𝑎 -- (7)

𝑓𝑜𝑟 𝑓𝑢𝑙𝑙 𝑏𝑎𝑠𝑖𝑐 𝑐𝑜𝑙𝑜𝑟 𝑓𝑟𝑜𝑚 𝑒𝑞𝑢𝑎𝑡𝑖𝑜𝑛 , 𝑖𝑓:

 [𝐻3𝑂+][ ln−]
𝑘𝑎= [𝐻ln]

𝐾𝑎
[𝐻3 𝑂+ ] = Eqtn 8
10

Indicator range is given from equations 7 and 8 by taking the negative log of the 2 equations:
𝑘𝑎
- log [𝐻 𝑂+] = − log 10𝑘 𝑡𝑜 − log
3 𝑎 10

- log [𝐻3𝑂+] = 𝑝𝐻 = − log 10 − log 𝑘𝑎 𝑡𝑜 − 𝑙𝑜𝑔10−1 − log 𝑘𝑎

= −1 + 𝑝𝑘𝑎 𝑡𝑜 (+1) −log 𝑘𝑎

𝑝𝐻 = −1 + 𝑝𝑘𝑎 𝑡𝑜 + 1 + 𝑝𝑘𝑎

Therefore 𝑝𝐻 𝑟𝑎𝑛𝑔𝑒 = 𝑝𝑘𝑎 ± 1 which means 𝑝𝐻 𝑟𝑎𝑛𝑔𝑒 = 4 𝑡𝑜 6 𝑖. 𝑒 4 − 6

So the pH in going from one color to the other has changed from pKa – 1 to pKa + 1. This is a

pH change of 2, and most indicators require a transition range of about two pH units. During

this transition the observed color is a mixture of the two colors. Midway in the transition, the

concentrations of the two forms are equal, and pH = pKa . Obviously, then the pKa of the

indicator should be close to the pH of the equivalence point.

There are 3 major types of acid base titrations

(i) Strong acid vs strong base

(ii) Strong acid vs weak base

(iii) Weak acid vs. strong base

Choice of an Indicator for an acid-base titration

An indicator for an acid base titration must fulfil two main conditions:

✓ It must undergo a readily detectable color change for the addition of a very small

quantity of titrant

✓ The color change must occur at (or very close to) the equivalence point.
The Table below shows the list of indicators suitable for different types of acid-base

titrations.

ype of Titration Suitable Indicator

Strong acid-strong base Any indicator-methyl orange, bromothymol

blue, phenolphthalein etc

Weak acid-strong base Phenolphthalein

Strong acid-weak base Methyl orange, bromothymol blue

Weak acid-weak base None (titration curve has no vertical section

at equivalence point so the first condition

above is not satisfied)

TITRATION CURVES

Titration curve for acid-base reactions is a plot of pH (or pOH) against milliliters of titrant.

It is a plot showing the change in pH of the solution in the conical flask as the reagent is

added from the burette.

(a) Strong acid Vs. strong base

Note that bcause it is a strong acid-base reaction, ionization is complete and the reaction can

be simplified as: H+ (aq) + OH- (aq) H2O (l)

100 mL of 0.1 M HCl Vs 100 mL of 0.1M NaOH

Assume initially (zero/no titration): 𝑝𝐻 = − log 10−1 = 1

𝐴𝑡 90% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛, 𝐻𝐶𝑙 𝑙𝑒𝑓𝑡 = 10%

10
⇒ 𝑝𝐻 = −𝑙𝑜𝑔 𝑥 0. 1 = −𝑙𝑜𝑔10−2 = 2
100
𝑎𝑡 99% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛, 𝐻𝐶𝑙 𝑙𝑒𝑓𝑡 = 1%
1 𝑥 0.1
⇒ 𝑝𝐻 = − 𝑙𝑜𝑔 = −𝑙𝑜𝑔10−3 = 3
100

𝑎𝑡 99.9% 𝑡𝑖𝑡𝑟𝑎𝑡𝑖𝑜𝑛, 𝐻𝐶𝑙 left = 0.1%

0.1 𝑥 0.1
⇒ 𝑝𝐻 = −𝑙𝑜𝑔 = −𝑙𝑜𝑔10−4 = 4
100

𝑖𝑓 100.1𝑚𝑙 𝑜𝑓 N𝑎𝑂𝐻 𝑖𝑠 𝑢𝑠𝑒𝑑 ⇒ 0.1𝑚𝑙 of NaOH was in excess

0.1 0. 1
⇒ 𝑝𝑂𝐻 = −𝑙𝑜𝑔 𝑥 = 4
100 1

Recall that pH + pOH = 14

Therefore 𝑝𝐻 = 14 − 4 = 10

𝐻𝑒𝑛𝑐𝑒 𝑝𝐻 = 1 (𝑖𝑛𝑖𝑡𝑖𝑎𝑙𝑙𝑦 0 𝑚L)

𝑝𝐻 = 2 (90 𝑚L)

𝑝𝐻 = 4 (99.9 𝑚L)

Below is an example of titration curve of a strong base added to a strong acid of same

molarity (e.g. using mL 0.1M NaOH added to 50 mL 0.1 M HCl)

mL 0.1M NaOH added

*Note that the pH range is (4-10) which is so large that all the indicators can usually be

used to follow the titration (Any indicator will do)

Titration curve for a Weak acid vs. strong base e.g. Acetic acid vs Sodium hydroxide

0.1 M 100 mL Acetic acid vs 0.1M 100 mL NaOH

HOAC + NaOH = NaOAC + H2O

Note that acetic acid (HOAC or CH3COOH) is a weak acid hence ionization is

incomplete.

- The initial pH cannot be 1

1. Hence consider the Kac HOAC = H+ + OAC-

[𝐻+][𝑂𝐴𝐶−]
𝐾 = = 1.75 𝑥 10−5 (𝐾 𝑓𝑜𝑟 𝑎𝑐𝑒𝑡𝑖𝑐 𝑎𝑐𝑖𝑑)
𝐴𝐶 [ 𝐻𝑂𝐴𝐶] 𝑎

𝑙𝑒𝑡 [𝐻+] 𝑎𝑛𝑑 [𝑂𝐴𝐶−] 𝑏𝑒 𝑡𝑎𝑘𝑒𝑛 𝑡𝑜 𝑏𝑒 𝑥 𝑟𝑒𝑠𝑝𝑒𝑐𝑡𝑖𝑣𝑒𝑙𝑦 ⇒ [𝐻𝑂𝐴𝐶]) = 𝑐 − 𝑥 at

equilibrium

But x <<< c

𝑇ℎ𝑒𝑟𝑒𝑓𝑜𝑟𝑒 𝑐 − 𝑥 = 𝑐

𝑥2
𝐾𝑎𝑐 =
𝑐

𝑥2
1.75 𝑥 10−5 =
0.1

𝑥 = √1.75 𝑥10−6 = 0.00132

𝑝𝐻 = − log 0.00132

= 2.878 = 2.88 𝑎𝑡 𝑖𝑛𝑖𝑡𝑖𝑎𝑙 𝑠𝑡𝑎𝑔𝑒

2. 𝐵𝑢𝑡 𝑎𝑡 𝑚𝑖𝑑 𝑝𝑜𝑖𝑛𝑡 50/50

[𝑂𝐴𝐶−] = [𝐻𝑂𝐴𝐶]
 [𝑎𝑐𝑖𝑑]
⇒ 𝑝𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔
[𝑠𝑎𝑙𝑡]

[50]
𝑝𝐻 = 𝑝𝐾𝑎 − 𝑙𝑜𝑔 [50]

𝐵𝑢𝑡 𝑝𝐾𝑎 = −𝑙𝑜𝑔𝐾𝑎 = − log 1.75 𝑥 10−5

𝑝𝐻 = −𝑙𝑜𝑔1.75 𝑥 105 − log 1

𝑝𝐻 = 4.757 𝑎𝑡 𝑡ℎ𝑒 𝑚𝑖𝑑 𝑝𝑡

3. The point of abrupt change in pH starts from where we add 0.1 mL of free HOAC

to 0.1 mL of free NaOH.

If 99.9 mL of NaOH was added we have 0.1 mL free HOAC

⇒ 99.9 𝑚L 𝑜𝑓 𝐻𝑂𝐴𝐶 𝑚𝑢𝑠𝑡 ℎ𝑎𝑣𝑒 𝑏𝑒𝑒𝑛 𝑎𝑑𝑑𝑒𝑑.

0.1
⇒ 𝑝𝐻 = −𝑙𝑜𝑔𝐾𝑎 − log
99.9

⇒ 𝑝𝐻 = 𝑝𝐾𝑎 + 3

𝑝𝐻 = 7.77 ≈ 8: ⇒ 𝑡ℎ𝑒 𝑝𝑜𝑖𝑛𝑡 𝑎𝑡 𝑤ℎ𝑖𝑐ℎ 𝑡ℎ𝑒 𝑎𝑏𝑟𝑢𝑝𝑡 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑝𝐻 𝑠𝑡𝑎𝑟𝑡𝑠.

4. 𝑆𝑢𝑝𝑝𝑜𝑠𝑒 𝑤𝑒 ℎ𝑎𝑣𝑒 0.1𝑚L 𝑓𝑟𝑒𝑒 𝑁𝑎𝑂𝐻 ⇒ 𝑤𝑒 ℎ𝑎𝑣𝑒 0.1% 𝑁𝑎𝑂𝐻 𝑙𝑒𝑓𝑡

0.1 0.1
⇒ 𝑝𝑂𝐻 = − log 𝑥 =4
100 1

𝑝𝑂𝐻 = 4,

𝑝𝐻 = 14 − 4 = 10

pH range is 8-10 hence limited number of indicator can be used to follow the titration.

Below Is the Titration curve of a weak acid vs strong base:

 Volume (mL) of 0.1M NaOH to the acid

*Note from the curve that the pH range is narrow (8-10) hence limited number of

indicators can be used to follow the titration. Likely indicator = phenolphthalein.

Strong acid Vs. weak base e.g. HCl Vs. NH4OH

𝑝𝐾(𝑁𝐻4𝑂𝐻)=1.85 𝑥 10−5

[𝑂𝐻] = √𝐾𝑏𝑎𝑠𝑒𝐶𝑏𝑎𝑠𝑒

𝑝𝐻 = 14 − 𝑝𝑂𝐻

The abrupt pH range at transition state is 4.0 - 6.74 which falls in the acid region.
Because the pH transition range is narrow, hence choice of indicator is restricted.

- Another disadvantage of this is that the end point cannot be sharp/satisfactory, hence we can
have titration error.
- This is the case with Kjedah analysis method of N2 determination. In which case instead of
titrating weak base NH4SO4with strong acid, we dissolve in strong acid and back titrate with strong
base.
The indicators that can follow this reaction are: methyl orange & methyl red. Below is the titration
curve for titration involving strong acid vs weak base:
 mL of 0.1M of NH4OH

*Note from the curve that the pH range is narrow (4-6.74) hence limited number of

indicators can be used to follow the titration.

Weak Acid vs weak base e.g. CH3COOH vs NH4OH

In this case, the pH change in the region of the equivalence-point is very much less than

sharp than in the previous examples and there is no vertical section in the curve.

Therefore, the equivalence point depends on the relative strengths of the weak base and

the weak acid being used which both have Ka =Kb giving an equivalence point of
pH = 7. Hence it is difficult to monitor the end point and therefore no indicator can

be used to detect the end point.

Titration curve for weak acid vs weak base