Chapter 5

TITRIMETRIC METHODS
OF ANALYSIS
 1. Redox titration
Permanganate (KMnO4) method
 Principle
 Conditions of reactions
 Standard potentials
 pH, t°, catalyst
Dichromate (K2Cr2O7) method
Iodimetry (I2: Iodine)
Iodometry (Iˉ: iodide ion)
 Redox titration
KMnO4 method
MnO4ˉ + 8H+ + 5e → Mn2+ + 4H2O Eo = 1.51 V
2CO2 + 2e → C2O42ˉ Eo = -0.49 V
2MnO4ˉ + 5C2O42ˉ + 16H+ → 2Mn2+ + 10CO2 + 8H2O

MnO4 : purple (at beginning)  Mn2+ : colourless (at

equivalence point)

Direct titration ***Note:

- Heating to ~ 70°C is necessary for titration
- Mn2+: as catalyst for titraction reaciton

CN(KMnO4) x VKMnO4 = CN(H2C2O4) x VH2C2O4

Redox titration
KMnO4 method
 Redox titration
K2Cr2O7 method
Cr2O72ˉ + 6Fe2+ + 14H+ → 2Cr3+ + 6Fe3+ + 7H2O
E°Cr2O72-(H+)/Cr3+ = 1.33 V; E°(Fe3+/Fe2+) = 0.77 V

Direct titration
- Indicator: Diphenylamine (DPh): Reducing
form (colourless)  Oxidising form (purple)

NOE (FeSO4) = NOE (K2Cr2O7)

CN(FeSO4) x VFeSO4 = CN(K2Cr2O7) x VK2Cr2O7
CN(FeSO4) = CN(K2Cr2O7) x VK2Cr2O7/VFeSO4 = [FeSO4]
Cg/l(FeSO4) = M(FeSO4) x [FeSO4]
 Redox titration
K2Cr2O7 method
Cr2O72ˉ + 9Iˉ + 14H+ → 2Cr3+ + I3ˉ + 7H2O
I3ˉ + 2S2O32ˉ → 3Iˉ + S4O62ˉ
Indirect titration Step 1: Formation of I3ˉ
Step 2: Titrating I3ˉ by Na2S2O3(aq) using starch
indicator

NOE (Na2S2O3) = NOE (K2Cr2O7)

CN(Na2S2O3) x VNa2S2O3 = CN(K2Cr2O7) x VK2Cr2O7
CN(Na2S2O3) = CN(K2Cr2O7) x VK2Cr2O7/VNa2S2O3 =
[Na2S2O3]

Cg/l(Na2S2O3) = M(Na2S2O3) x [Na2S2O3]

Redox titration
K2Cr2O7 method
 Redox titration
Iodimetry

 In iodimetry, the titrant is I2 and the analyte is a reducing

agent. The end point is detected by the appearance of the
blue starch–iodine color.
 Too acidic, the starch hydrolyze or decompose  affect the
end point
 Too alkaline, I2 will disproportionate:
I2 + OH  I + IO + H2O
Iodine has a low solubility in water but the complex I3− is very
soluble. So iodine solutions are prepared by dissolving I2 in a
solution of potassium iodide where iodide is present in a large
excess:
I 2 + I − → I 3−
Therefore, I3− is the actual species used in the titration.
 Q&A
The level of dissolved oxygen in a water sample is determined by
the Winkler method. In a typical analysis a 100.0-mL sample is
made basic and treated with a solution of MnSO4, resulting in the
formation of MnO2. An excess of KI is added and the solution is
acidified, resulting in the formation of Mn2+ and I2. The liberated I2 is
titrated with a solution of 0.00870 M Na2S2O3, requiring 8.90 mL to
reach the starch indicator end point. Calculate the concentration of
dissolved oxygen as parts per million O2 (6.21 ppm).

The thickness of the chromium plate on an auto fender is

determined by dissolving a 30.0-cm2 section in acid and oxidizing
Cr3+ to Cr2O72- with peroxydisulfate. After removing excess
peroxydisulfate by boiling, 500.0 mg of Fe(NH4)2(SO4)2•6H2O is
added, reducing the Cr2O72- to Cr3+. The excess Fe2+ is back
titrated, requiring 18.29 mL of 0.00389M K2Cr2O7 to reach the end
point. Determine the average thickness of the chromium plate given
that the density of Cr is 7.20 g/cm3 (6.9x10-5 cm)
 2. Acid - Base titration
 Titrating a strong acid with a strong base
- Reaction
- pH at the equivalence
- Indicator
 A weak acid with a strong base
 A weak base with a strong acid
 A polyprotic acid with a strong base
 A polyprotic base with a strong acid
 A mixture of bases with a strong acid
 Acid - Base titration
Strong acid & Strong base titration

 pHeq = 7
 Any indicator with pH range of
colour change: ~ 3-10

11
 PHENOLPHTHALEIN

Colourless Pink

pH range of colour
change
(8.2 – 10)
 Acid - Base titration
Strong acid & Strong base titration
 Acid - Base titration
Strong acid & Strong base titration
 Acid - Base titration
Weak acid & Strong base titration

HA + NaOH  NaA + H2O pHeq = 7 + (pKHA + lgCNaA)/2

Indicator •Phenolphthalein
• Thymolphthalein
16
 Acid - Base titration
Strong acid & Weak base titration

A- + HCl  HA + Cl- pHeq = 7 + (pKHA - lgCHA)/2

Indicator
• Methyl red
• Bromocresol green
• Methyl orange

17
 Acid - Base titration
polyprotic acid with a strong base
H 3 PO4  H   H 2 PO4 , K a1 10 2.12
pHeq1 =1/2 (pKa1 +pKa2) = 4.7
H 2 PO4  H   HPO42 , K a 2 10 7.21 pHeq2 =1/2 (pKa2 +pKa3) = 9.8
HPO42  H   PO43 , K a 3 10 12.38
• 2V1 = V2: H3PO4
0
• 2V1 > V2 : mixture H3PO4 & strong acid
1
0
2
• 2V1 < V2 : mixture H3PO4 & weak acid
0
pH (OH   H 2PO4  HPO24  H 2O)
3
0 Burette
(NaOH) 4 (C) Phenolphthalein
0 9.8 Colourless – Pink (8.2 – 10.0)
5
0

4.7 (OH  H3PO4  H2PO4  H2O)

Bromocresol green
Yellow – Blue (3.8 – 5.4)
Erlen
(X) VNaOH, mL
(H3PO4)
V1 V2
 Acid - Base titration
polyprotic acid with a strong base
 Acid - Base titration
polyprotic acid with a strong base
 Acid - Base titration
polyprotic base with a strong acid

2-
Stepwise titration:
Titrating CO3 with HCl
Difference in Ka ≥ 104 times
CO32- + H+ HCO3-
HCO3- + H+ H2CO3 *if one is strong acid/base,
Ka(b) of weak acid/base: ≤ 10-5

pHeq1 =1/2 (pKa1 + pKa2) = 8.3

pHeq2 =1/2 (pKa2 - lgC) ~ 4.0

- Phenol phthalein → Veq1

- Methyl red/Bromophenol blue

→ Veq2
Veq2 = 2Veq1 21
 Acid - Base titration
polyprotic base with a strong acid
 Q&A
1. Samples that contain a mixture of the monoprotic weak
acids 2–methylanilinium chloride (C7H10NCl, pKa=4.447)
and 3–nitrophenol (C6H5NO3, pKa= 8.39) can be analyzed
by titrating with NaOH. A 2.006-g sample requires 19.65
mL of 0.200 M NaOH to reach the bromocresol purple
end point and 48.41 mL of 0.200 M NaOH to reach the
phenolphthalein end point. Report the %w/w of each
compound in the sample (39.8% w/w).
2. A mixture of HCl and H3PO4 is titrated with 0.1000 M
NaOH. The first end point (methyl red) occurs at 35.00
mL, and the second end point (bromthymol blue) occurs
at a total of 50.00 mL (15.00 mL after the first end point).
Calculate the millimoles HCl and H3PO4 present in the
solution. (H3PO4: 1.5 mmol; HCl: 2 mmol)
 3. Precipitation Titration
 Morh’s method
 Reaction
 Indicator
 Conditions
 pH
 to
 Fajans’ method
 Volhard’s method
 PRECIPITATION TITRATION
C + X  CX 

Solution of C Unknown concentration ion (X)

 Ag+(aq): AgNO3  Br, Cl, I
 Hg2+(aq) or Hg+(aq) CN-, SCN-

reacting with titrant to form coloured

precipitate
Indicator Adsorption indicator
reacting with titrant to form coloured complex
High rate of precipitation
Conditions
Ksp(CX) is small (< 107 – 10 8 )
25
 PRECIPITATION REACTION
Mohr’s method
Direct titration: determining concentration of halogen by
titration with standard silver nitrate solution.
A soluble chromate salt is added as the indicator

Titration reaction: Ag+ + X-  AgX

Reaction with indicator: 2Ag+ + CrO42-  Ag2CrO4  (red-brown)

This method can be used to determine the chloride ion

concentration in neutral or unbuffered solutions

Condition: pH of the sample solutions should be 6.5 – 10

26
 PRECIPITATION REACTION
Mohr’s method

pH < 6.5 2CrO42 + 2H+  2HCrO4  Cr2O72 + H2O

more Ag+ will be required to form the Ag2CrO4 precipitate

pH > 10 2Ag+ + 2OH  2AgOH  Ag2O  + H2O

silver hydroxide may be precipitated and brown Ag2O

obscures the red Ag2CrO4 precipitate color
In actual practice:
 The indicator concentration is kept at 0.002 to 0.005 M

 Titration should be performed at room temperature (solubility

of Ag2CrO4 increases at high to) 27
PRECIPITATION REACTION
Mohr’s method
 PRECIPITATION REACTION
Mohr’s method

+ Ag+

Before addition of Before After

endpoint
AgNO3, chromate endpoint endpoint
indicator + solution
 lemon-yellow
slight stronger
cloudy red- red-
solution brown brown
 PRECIPITATION REACTION
Fajans’ method
Direct titration: determination of halogen (Cl-, Br-, I- ) by titration
with standard AgNO3(aq) in presence of adsorption indicator
The indicator, which is a dye, exists in solution as the ionized
form, usually an anion
Titration reaction: Ag+ + X-  AgX

Reaction with indicator (for ex, anionic dye dichlorofluoroscein):

AgX.X  AgX  AgX. Ag+Fl (pink)

pH = 6,5 – 10: pH < 6,5  Fl + H+  HFl

Condition [X]0  10  2M  AgX for colour vision
Adding dextrin to prevent coagulation of AgCl
30
 PRECIPITATION REACTION
Volhard’s method
Back titration: finding concentration of halogen by titration with
excess standard AgNO3(aq). Then, excess Ag+ is determined in
a titration with standard KSCN(aq) in the presence of Fe3+(aq)
indicator.

Ag+ + X-  AgX + excess Ag+

Titration reaction: excess Ag+ + SCN-  AgSCN

Reaction with indicator: Fe3+ + SCN  Fe(SCN)2+ (red)

Condition: pH of the sample solutions should be < 3.

32
 PRECIPITATION REACTION
Volhard’s method
***Note
TAgSCN (10-11.97) < TAgCl (10-9.75)  AgCl + SCN  AgSCN
AgCl is dissolved  AgCl need to be filtrated before titration
 Complexation Titrations
 Reaction
 Conditions
 Applications
 Determine concentration of Ca2+, Mg2+ or
mixture of Ca2++Mg2+ in water (water
hardness)
 Determine concentration of Al3+, Fe3+ or
mixture of Al3++ Fe3+ in water
Complexation Titrations

- Titrant: Ethylenediaminetetraacetic
acid (EDTA)
- Form of EDTA used: Na2H2
(complexon III or Trilon B), H22 or
4.
H22 + Mn+ ⇄ Mn4 + 2H+
- Condition: suitable pH and indicator

35
 Complexation Titrations
Titration of Mg2+, Ca2+ with EDTA, pH = 10
1/ Titration of Mg2+ or mixture of (Mg2+, Ca2+)

 pH = 10,
 Indicator: Eriochrome Black T (HIn)

Titration reaction:
Mg2+ + 4 ⇄ Mg2
Ca2+ + 4 ⇄ Ca2

Reaction with MgIn + 4 ⇄ Mg2 + Inˉ

indicator CaIn + 4 ⇄ Ca2 + In ˉ
 Complexation Titrations
Titration of Mg2+, Ca2+ with EDTA, pH = 12.5
2/ Titration of Ca2+
 pH = 12.5
 Indicator: Fluorexone (HIn)
At pH = 12.5  [OHˉ] = 10-1.5 M
[Mg2+][OHˉ]2 ~ 10-3 x (10-1.5)2 ~ 10-6 > 10-9.22 = KspMg(OH)2
 Precipitate [Mg(OH)2]
HIn + Ca2+, Mg2+  Ca2+, Mg(OH)2, CaIn

Titration reaction: Ca2+ + 4 ⇄ Ca2

Reaction with indicator:

CaIn + 4 ⇄ Ca2 + In ˉ
 Complexation Titrations
Titration of Mg2+, Ca2+ with EDTA, pH = 12.5
2/ Titration of Ca2+
 Complexation Titrations
Titration of Fe3+, Al3+ with EDTA
1/ Titration of Fe3+ (in mixture with Al3+)

 pH = 2.5 and [Fe3+] ≤ 10-3 (to prevent formation of Fe(OH)3)

 Indicator: sulfosalicyclic acid (HIn)

In the conical flask: HIn + Fe3+, Al3+  Fe3+, Al3+, FeIn

Titration reaction: Fe3+ + Y4 ⇄ FeYˉ
***Reaction is slow  slowly titrate and heat gently

Reaction with indicator:

FeIn + Y4 ⇄ FeY (pale yellow) + Inˉ (colourless)
 Complexation Titrations
Titration of Fe3+, Al3+ with EDTA
1/ Titration of Fe3+ (in mixture with Al3+)
 Complexation Titrations
Titration of Fe3+, Al3+ with EDTA
2/ Titration of Al3+
 Back titration, 80°C; Indicator: PAN
 pH = 5 (adding buffer pH 5 to solution pH 2.5 in part 1)
Y4-
Al3+
Cu
In the conical flask: Excess Y4- + FeY ˉ, Al3+  FeY ˉ, AlYˉ, Y4ˉ
Titration reaction: Cu2+ + Y4 ⇄ CuY2-
Reaction with indicator: Cu2+ + Inˉ ⇄ CuIn

green yellow pink violet

Adding
bromocreseol green blue blue
 Complexation Titrations
Titration of Fe3+, Al3+ with EDTA, pH = 2.5
2/ Titration of Al3+ (in mixture with Al3+)
 Complexation Titrations
Titration of Fe3+, Al3+ with EDTA, pH = 2.5
2/ Titration of Al3+ (in mixture with Al3+)
 Q&A

Before the introduction of EDTA most complexation titrations used

Ag+ or CN– as the titrant. The analysis for Cd2+, for example, was
accomplished indirectly by adding an excess of KCN to form
Cd(CN)24-, and back titrating the excess CN– with Ag+, forming
Ag(CN)2- . In one such analysis a 0.3000-g sample of an ore is
dissolved and treated with 20.00 mL of 0.5000 M KCN. The excess
CN– requires 13.98 mL of 0.1518 M AgNO3 to reach the end point.
Determine the %w/w Cd in the ore. (53.9 %w/w)
Solutions that contain both Fe3+ and Al3+ are selectively analyzed for Fe3+
by buffering to a pH of 2 and titrating with EDTA. The pH of the solution is
then raised to 5 and an excess of EDTA added, resulting in the formation
of the Al3+–EDTA complex. The excess EDTA is back-titrated using a
standard solution of Fe3+, providing an indirect analysis for Al3+.
(a) At a pH of 2, verify that the formation of the Fe3+–EDTA complex is
favorable, and that the formation of the Al3+–EDTA complex is not
favorable.
(b) A 50.00-mL aliquot of a sample that contains Fe3+ and Al3+ is
transferred to a 250-mL Erlenmeyer flask and buffered to a pH of 2. A
small amount of salicylic acid is added, forming the soluble red colored
Fe3+–salicylic acid complex. The solution is titrated with 0.05002 M EDTA,
requiring 24.82 mL to reach the end point as signaled by the
disappearance of the Fe3+–salicylic acid complex’s red color. The solution
is buffered to a pH of 5 and 50.00 mL of 0.05002 M EDTA is added. After
ensuring that the formation of the Al3+–EDTA complex is complete, the
excess EDTA is back titrated with 0.04109 M Fe3+, requiring 17.84 mL to
reach the end point as signaled by the reappearance of the red-colored
Fe3+–salicylic acid complex. Report the molar concentrations of Fe3+ and
Al3+ in the sample. (0.03536 M)