6.

Screened, Mixed and Universal Indicators

Screened Indicators. A mixture of an indicator and a dye for more sharper colour
change (methyl orange & indigo carmine: colour changes (at pH 4.1) from green
(in alkaline) to violet (in acid).
Mixed indicators. A mixture of two indicators having similar pH range but
showing contrasting colour.

Composition Acidic colour Basic colour pH

Bromocresol blue : Methyl red Red Green 5.1
Neutral red : Methylene blue Blue-violet Green 7.0
Phenolphthalein : -Naphtholphthalein Pale pink Violet 8.9
Thymol blue : Phenolphthalein Yellow Violet 9.0

Universal (multi-range) indicators. A mixture of indicators, its colour change extends

over a considerable pH range. Used for rough determination of pH, but not suitable
for titration.
 Colour indicators cannot be used if coloured solutions
are to be titrated. End point in such cases can be
detected either potentiometrically or by the use of
turbidity or fluorescence indicators.
2- Turbidity indicators
Many higher organic acids or bases form colloidal
solutions, which at certain pH, form flocculent
precipitates. They are used when titrating a dark
coloured solution.
3- Fluorescence indicators
Certain compounds emit visible radiations when
exposed to UV light, this property may stop or
intensify, when certain pH is reached. They are used
with coloured or turbid solutions, e.g. umbelliferone
indicator.
 Neutralization (Acid-Base) Titration Curves

- The titration curve is a plot of pH values versus the volume of titrant.

- They are constructed to study the feasibility of the titration and to help in
choosing an indicator for the titration.
- Graphical determination of the End Point and the pH at this point.
1. Strong Acid – Strong Base (HCl – NaOH) 40.0 mL of 0.1 M HCl
 Before addition of any NaOH:
pH = pCa = — log [H+] = — log 0.1 = 1
 After addition of 10 mL of NaOH:
pH = pCa = — log [H+] = — log (0.1 30 / 50) = — log 0.06 = 1.22

 After addition of 20 mL of NaOH:

pH = pCa = — log [H+] = — log (0.1 20 / 60) = — log 0.033 = 1.48
 After addition of 30 mL of NaOH:
pH = pCa = — log [H+] = — log (0.1 10 / 70) = — log 0.014 = 1.85

 After addition of 40 mL of NaOH (at the equivalence point):

pH = pOH = ½ pKW =7.0
 After the equivalence point (after addition of 50 mL NaOH):
pH = pKW – pCb = 14 – ( — log 0.110/90)
pH = 14 – ( — log 0.01) = 14 – 1.95) = 12.05
 AY

PP

PR

MR

MO

Titration Curve for Strong Acid – Strong Base (HCl – NaOH)

2. Weak Acid – Strong Base (HOAC – NaOH) 40.0 mL of 0.1 M HOAC
 Before addition of any NaOH:
pH = ½ pKa + ½ pCa = ½ (4.74) + ½ ( — log 0.1) = 2.37 + 0.5 = 2.87

 After addition of 20 mL of NaOH (Buffer):

pH = pKa + log [salt] / [acid] = 4.74 + log 1 = 4.74 + 0 = 4.74

 After addition of 40 mL of NaOH (at the equivalence point):

pH = ½ pKW + ½ pKa – ½ pCs = 7 + 2.37 – ½(1.3) = 8.72

 After the equivalence point (after addition of 50 mL NaOH):

pH = pKW – pOH = 14 – (- log 0.110/90)
pH = 14 – ( — log 0.01) = 14 – 1.95) = 12.05
 pKa

Titration Curves for Strong Acid ( – ) or Weak acid ( – ) with Strong Base
Effect of Ka on the shape of the titration curve of titration of 0.10 M acid
3. Weak Base – Strong Acid (NH4 OH – HCl) 40.0 mL of 0.1 M NH4OH

 Before addition of any HCl:

pH = pKW – ½ pKb – ½ pCb =
pH = 14 – ½ (4.74) – ½ ( — log 0.1) = 14 – 2.37 – 0.5 = 11.13

 After addition of 20 mL of HCl (Buffer):

pH = pKW – pKb + log [base] / [salt] = 14 – 4.74 + log (1 )
pH = 9.26 + 0 = 9.26

 After addition of 40 mL of HCl (at the equivalence point):

pH = ½ pKW – ½ pKb + ½ pCs = 7 – 2.37 + ½(1.3) = 5.28

 After the equivalence point (after addition of 60 mL HCl):

pH = – log [H+] = – log (0.1 20 / 100) = 1.7
 pKb

Titration Curve for Weak Base – Strong Acid (NH4 OH – NaOH)

4. Polybasic Acid with Strong Base (H3 PO4 and NaOH)

H3PO4 + OH H2PO4 + H2O (k1 = 7.0  103 )

H2PO4  + OH HPO42 + H2O (k2 = 7.0  108 )
HPO4 2 + OH PO43 + H2O (k2 = 5.0  1013 ) Not feasible

Titration of diprotic acid (H2A) with NaOH

 Titration of 100 mL of diprotic acid (H2A) with NaOH

 pH at 1 st E.P. = ½ (pK1 + pK2 ) = ½ (2.12 + 7.12) = 4.66 (M.O.)

 pH at 2 st E.P. = ½ pKW + ½ pKa — ½ pCs = 9.94 (Ph.Ph.)