6/23/21

HANOI NATIONAL UNIVERSITY OF EDUCATION

FACULTY OF CHEMISTRY

Analytical Chemistry 2
Quantitative Chemical Analyses

Course contents

S Chapter 1: The analytical Process (1)

S Chapter 2: Chemical Measurements and Experiment Error (1)

S Chapter 3: Titrations in Analytical Chemistry (1)

S Chapter 4: Acid-Base titrations (7+3)

S Chapter 5: EDTA titrations (4+2)

S Chapter 6: Precipitation titrations (3+1)

S Chapter 7: Redox titrations (5+2)

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Course Schedule
Class Topic Chapter [2] No. of lesson Exam

1 Introduction to Quantitative Chemical Analysis and Volumetric 0-3 3 Quiz

Titration

2 Acid-Base titrations 10 3
3 Exercise acid-base part 1 10 2
Acid-Base titrations (cont.) 1

4 Acid-Base titrations (cont.) 10 1

Exercise acid-base part 2 2

Date: 8th July; Time will be proposed Exam 1

5 EDTA titrations 11 3
6 EDTA titrations (cont.) 11 1
Exercise EDTA titration 2

7 Precipitation titrations 26 3
8 Precipitation titrations (cont.) 26 3
Date: 24 Jul; Time will be proposed Exam 2

9 Redox titration 15 3
10 Redox titration (cont.) 15 1
Exercise Redox titration 2
Review course
Date: 31 Jul; Time will be proposed Exam 3

Textbooks

[1] Douglas A. Skoog, Donald M. West, F. James Holler. Fundamentals of

Analytical Chemistry, 9th edition, 2014, USA

[2] Daniel C. Harris. Quantitative Chemical Analysis, 8th edition, 2010, USA

[3] Nguyễn Tinh Dung, Hoá học phân tích III, Các phương pháp định lượng
hoá học, NXBGD Hà Nội, 2000

[4] Đào Thị Phương Diệp, Đỗ Văn Huê. Hóa học phân tích 3. Các phương
pháp định lượng hóa học. NXBĐHSP Hà Nội 2007

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1 The Analytical Process

1.1 Procedure of Analyses

2 Chemical Measurements
Experiment Error

II.1. Units of concentration

1. Molarity and Normality.
2. Calculation based on molar and equivalent concentrations.

II.2. Parameters of analytical measurement

1. Accuracy and precision
2. Systematic and random errors.
3. Mean, median and variance.

II.3. Representation of results of measurements

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II.1. Unit of Concentration

S Molarity, M = mole solute/liter of solution

S Normality, N = equivalents of solute/liter of solution

S Weight percent, Wt%, w/w = (mass of solute/mass of solution)x100%

S Mass per volume, mg/L = mass of solute/liter of solution

S Parts per million, ppm = (mass of solute/mass of solution)x10 6

10

II.1. Unit of Concentration

Unit Solution Solid

ppm …/L μg/mL mg/kg

ppb μg/L ng/… …/kg

ppt ng/… …/mL ng/kg

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II.1. Unit of Concentration

S How to convert concentration in mg/L to molarity, and vice

versa?

S What is the molarity of a 6.2 mg/L solution of O2 (aq)?

S The Maximum Acceptable Concentration (MAC) of Pb in drinking
water is 10 ppb. If sample has concentration of 55 nM, does it
exceed the MAC?
S Plants selectively synthesize normal alkanes with an odd number of
carbon atoms. The conc. of C29 H60 in summer rain-water collected in
Hanover, Germany is 34 ppb. Find the molarity of C29 H60 and
express the answer with a prefix.
12

II.1. Unit of Concentration

S Normality is defined as the number of equivalents of solute per liter.

S Eq. weight: EW = MW/K

S K = no. eq. per moles, K is an integer ≥ 1, N = K × M

S K is depend on the reaction type and the balance chemical reaction

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II.1. Unit of Concentration

Comp. Reaction K M.W. E.W.

HCl HCl + NaOH = NaCl + H2 O 1 36.5 …

Ba(OH)2 2HCl + Ba(OH)2 = BaCl2 + 2H2 O … 171.34 …

H3 PO4 H3 PO4 + NaOH = NaH2 PO4 + H2 O … 97,99 …

AlCl3 AlCl3 + 3NaOH = Al(OH)3 + 3 NaCl … … 44.45

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II.1. Unit of Concentration

Balanced half reaction K

Fe 3+ + 3e ! Fe 3

I2 + 2e ! 2 I– 2

2 S2O32- + 2e ! S4O62– …

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II.1. Unit of Concentration

Calculation based on Molarity and Normality

S Method 1: use the appropriate value of K to convert Molarity, and use

the coefficients in the balanced chemical equations to solve for the
number of moles of analyte in given sample volume.

S Method 2: use the normal concentrations directly ignoring the

coefficients in the balanced chemical reaction.

no. eq. analyte = no. eq. titrant

Then, the normality is converted to moles/L or mg/L using K or

E.W., respectively.

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II.1. Unit of Concentration

Calculation based on molar and equip. concentration

Problem 1: When 25.0 mL of NaOH solution was titrated, 23.4 mL of

0.286 M H2 SO4 were required to reach the end point. Find the molarity of
the NaOH.

2 NaOH + H2 SO4 → Na2 SO4 + 2H2 O

S Method 1: S Method 2:

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II.1. Unit of Concentration

Calculation based on molar and equip. concentration

Problem 2: The Winkler titration for the determination of dissolve oxygen

involves the treatment of the sample with iodine ion (I– ) in the presence of
manganese ion catalyst (Mn2+) as follow:

O2 + 2 Mn2+ + 2H2O → 2 MnO2(s) + 4 H+

MnO2(s) + 4 H+ + 2 I– → Mn2+ + I2 + 2H2O

The liberated iodine is then titrated with a standard thiosulfate solution.

I2 + 2S 2O32– → 2 I– + S 4O62–

A 50.00 mL sample of water was treated as above and the I2 titrated with
0.01136 N Na2 S 2 O3 , of which 8.11 mL were required to reach the end point.

Determination the conc. of the dissolved O2 in eq./L, moles/L and mg/L

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II.2. Parameters of analytical measurement

Accuracy vs Precision

S Accuracy : The closeness of a

measurement, or the mean of
multiple measurements, to its true or
accepted value.

S Precision: The agreement A B

between multiple measurements
made in the same way.

1. Low accuracy, high precision

2. High accuracy, low precision
3. High accuracy, high precision C D
4. Low accuracy, low precision
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II.2. Parameters of analytical measurement

Random vs Systematic Errors

S Random (indeterminate) error: causes data to be scattered

more or less symmetrically around a mean value.
Random error degrade Precision and does not influence Accuracy

S Systematic (determinate) error: causes the mean of a data set

to differ from the accepted value.
Systematic error degrade Accuracy and does not influence Precision

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II.2. Parameters of analytical measurement

Random vs Systematic Errors

S How to cancel random errors? Repeat the experiments

S How to know the result having systematic errors? Doing a determination

using a different method or Comparing results among different laboratories

S Give some examples of systematic errors and how to avoid these?

Use miscalibrated balances and glassware Periodically calibrate a balance

and use standard glassware
The purity of the reagents causing by the Kept reagents in low humidity
absorption of moisture from the ambient desiccators
air
The visual determination of the end point Use the appropriate indicator
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II.2. Parameters of analytical measurement

Expressing the result of chemical calculation

Significant figures in a number are all of the certain

digits plus the first uncertain digit

When reading a 50-mL burette 30.24 mL 4 significant

figures 0.03024 L or 3.024 × 10 -2 L

For the final chemical calculation, which expression is

correct?
0.032 ± 0.002 or 0.03245 ± 0.001786
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3 Titrations in Analytical Chemistry

Titration methods are based on measuring the amount of
a reagent of known concentration that is consumed by an
analyte in a chemical or electrochemical reaction.
Volumetric titrations involve measuring the volume of a
solution of known concentration that is needed to react
completely with the analyte.

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III.1. Some terms used in

Volumetric Titrations
The titration and titration reaction
(Requirements: speed, known
stoichiometry, suitable indicator)
A standard solution (standard titrant)
– known conc. – preparing by direct
method/standardization
Equivalence points (theoretical points)
and End points (experimental points)
Indicators and titration error
Titration curves
30

III.1. Some terms used in Volumetric Titrations

Titration curves
Absolute titration error:
Vf – Vep
Relative titration error:
End point q = (Vf – Vep)/ Vep
pH Vf
p-function

pM
pe Equiv. point Vep
pAg End point

Reagent volume
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III.1. Some terms used in Volumetric Titrations

Error
S Titration error: choice of an indicator whose change does not occur
sufficiently close to the equiv. point. – systematic error.
S Personal errors:
S Poor glassware gauging
S Reading error
S Wetting of the graduated flasks
S Not respecting the draining time
S Delivering any drop adhering to the out side of the pipette

S Random errors

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III.2. Standard solutions and Standardization

Requirements Concentration

S Sufficiently stable 1. Direct method:

S React rapidly with the analyte Dissolve Primary standard – solution

S React more or less completely 2. Standardization

with the analyte
Titrate a primary standard with the
S Undergo a selective reaction with standard solution
the analyte

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III.2. Standard solutions and Standardization

Primary standard H2C2O4.2H2O

(M = 126.064)
1. High purity.
2. Atmospheric stability. Na2B4O7.10H2O
(M = 381.4)
3. Absence of hydrate water so that the composition
of the solid does not change with variations in
humidity.
4. Reasonably large molar mass so that the relative
error associated with weighing the standard is
minimized.
5. Modest cost.
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III.3. Some techniques and Calculation in

Volumetric Titrations

Techniques Calculation
Direct titration: # eq. X = # eq. T
X+T→P
Back titration: #eq. X = #eq. R – #eq. T
X+R→P
Rexcess + T → Q
Replacement titration: #eq. X = #eq. Y = #eq. T
X+R→Y
Y+T→P
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III.3. Some techniques and Calculation in

Volumetric Titrations

S Example 1: The phosphorus in a 4.258-g sample of a plant food was

converted to PO4 3- and precipitated as Ag3 PO4 by adding 50.00 mL of
0.0820 M AgNO3 . The excess AgNO3 was back-titrated with
4.06 mL of 0.0625 M KSCN. Express the results of this analysis in
terms of % P 2 O5 .

S Example 2: A 1.080-g sample of a copper ore is dissolved in acid. An

unmeasured excess of a solution containing the KI is introduced into
the solution. The liberated iodine (replace for copper) is then
titrated with 15.56 mL of 0.0950 M Na2 S 2 O3 . Calculate the result of
this analysis in term of % Cu (63.546 g/mol).

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4 Acid – Base Titrations

S Which indicators can be
used in A-B titrations?
IV.1. Indicators pT and error
S Which acids or bases can
IV.2. Strong acids, bases be titrated?
pK, C
IV.3. Weak acids, bases
IV.4. Polyprotic acids and bases

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IV.1. Indicators for acid-base titrations

HIn ! In– + H+ Ka
Ka =
[H + ][In - ]
Acid color base color [HIn]

[HIn]
[H + ] = K a
– H3O+
pH [In − ]
!

Colorless Red
Phenolphthalein
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IV.1. Indicators for acid-base titrations

Ind. pH range
pKa ± 1

Phenolphthalein (pH range 8.0 – 10.0)

pT = 8
pT = 9
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IV.2. Titrations of Strong Acids and Bases

IV.2.1. Titrating a strong acid with a strong base
IV.2.1.1. Titration curve

S Generate the hypothetical titration curve for the titration of

10.00 mL of 0.1 M HCl with 0.1 M NaOH.

S Using the Charge-balance Equation to construct Titration curve

at 3 stage of the titration:
S Preequivancence
S Equivalence
S Postequivalence

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IV.3. Titrations of Weak Acids and Bases

IV.3.2. Titrating a week base with a strong acid
IV.3.2.1. Titration curve
IV.3.2.2. Titration error

14 " K %
pH C $C0α HA + (h − w )'
Titration curve CV # h &
12
P= =
C0V0 " K %
C0 $C − (h − w )'
# h &
10 Titration jump:
Narrow
HY 8
C, V Asymmetric, shift to an acid range
6
Dependent on C, C0, Ka

4
Error at point close to the equiv. point
2

0 # K & C + C0
0,8 0,9
P 1 1,1 q ≈ %h − w ( − α A−
$ h ' CC0
A– 47
C0 , V0

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REVIEW HY = XOH XOH = HY

Titration
curve

Titration
error
HA = XOH A– = HY
Titration
curve

Titration
error

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IV.4. Mixture of Strong and Weak Acids/Bases

IV.4.1. Condition of separately titration and titration curves

pH Titration curve: construct the titration

12
curve for the titration of 10 mL of the
10 mixture of 0.010 M HCl and 0.010 M
HA (Ka = 10-6 ) with 0.010 M KOH
8
HA when the volumes of base added are:
6 0.00, 6.00, 9.90, 15,00, and 19,90 mL

4 Ka changed – what’s happen???

HY Ka ??? – separately titrate
2

0
0 5 10 15 20 25
V
51

IV.4. Mixture of Strong and Weak Acids/Bases

IV.4.1. Condition of separately titration and titration curves

pH
12
General when C = C 0 = 0.01 M
10
9 5 < pKa < 9: titrate separately HY and HA
8
8 pKa < 5: titrate total HY and HA
9 < pKa : titrate HY, but HA
6
6
5

4
HY+HA HY then HA HY

2 5 9 pK
V
0
5 10 15 20 25 52

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IV.4. Mixture of Strong and Weak Acids/Bases

IV.4.1. Condition of separately titration and titration curves
IV.4.2. Titration errors

pH
At the 1st equiv. point
12

10 pK = 8

8 pK = 6

pK = 4 At the 2nd equiv. point

6

0
0,1 0,3 0,5 0,7 0,9 1,1
P

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IV.4. Mixture of Strong and Weak Acids/Bases

IV.4.1. Condition of separately titration and titration curves
IV.4.2. Titration errors

Example 1: A 10.00 mL solution that is 0.050 M in HCl and 0.040 M in

HA (Ka = 10-5 ) is titrated with 0.050 M KOH:
a. Calculate the pH at the 1st and the 2nd equiv. point.
b. Choose the most suitable indicators in Table 10.3 (page 221 [2]) for
the determination of the 1st and 2nd equiv. points.
c. Calculate the titration error when using methyl orange (pT=4.4) and
phenolphthalein (pT=9) as the indicators for the 1st and 2nd equiv.
points, respectively.

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IV.4. Mixture of Strong and Weak Acids/Bases

IV.4.1. Condition of separately titration and titration curves
IV.4.2. Titration errors

Example 2: In the titration of 10 mL of the mixture of HCl and HA (Ka

= 10-6 ) with 0.100 M KOH:
9.77 mL is required to reach a methyl yellow end point (pT=4)
18.65 mL is needed to reach a thymol blue end point (pT=9)
a. Calculate the practical concentration of HCl and HA.
b. Calculate the titration errors at 2 end points
c. Calculate the volume of 0.100 M KOH needed to titrate to a
phenolphthalein end point (pT=9.8).

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IV.5. Titrations of polyprotic Acids/Bases

IV.5.1. Titration curves

Titration of 20.00 mL of
0.10 M H2 A with 0.10 M NaOH

Ka1 / Ka2 > 104

Case: H2 A: maleic acid

Ka1 = 1.3 10-3 ; Ka2 = 5.9 10-7
Calculate the pH
at the 1st and 2nd equiv. points

Indicators:
Methyl yellow (pT=4)
Phenolphthalein (pT=9)
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IV.5. Titrations of polyprotic Acids/Bases

IV.5.1. Titration curves
IV.5.2. Titration errors

At the 1st equiv. point

At the 2nd equiv. point

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5 EDTA Titrations

S V.1. Complexes of EDTA and metal ions

S V.2. Titration curves and titration errors

S V.3. Indicators for EDTA titrations

S V.4. Titration methods involving EDTA

S V.5. Applications of EDTA titrations

V.1. Complexes of EDTA and metal ions

V.1.1. EDTA

EDTA

Complexon III – Titriplex III

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V.1. Complexes of EDTA and metal ions

V.1.1. EDTA
V.1.2. Complexes of EDTA and metal ions

ALL METALS; M : Y4- = 1 : 1; STABLE

Formation constants for EDTA Complexes
Cation log βMY log β’ MY
Ca2+ 10.70 9.42 (pH = 9)
… … …
Al3+ 16.13 8.90 (pH = 5)
Zn2+ 16.50 10.39 (pH = 9; [NH3] = 0.1 M)
… … …
Fe3+ 25.10 11.44 (pH = 2)

V.2. Titration curve and titration error

V.2.1. Titration curve

Direct titration Ca2+ with EDTA at pH 9.0

Titration reaction
EDTA
(Ca2+)’ + (Y4-)’ → CaY2- β’=109.42
C = 0.010 M
V = mL C0V0
= [Ca 2+ ]'+[CaY 2− ] (1)
V +V0
CV
= [Y 4− ]'+[CaY 2− ] (2)
V +V0
[CaY 2− ] (3)
Ca 2+ β'=
C0 = 0.020 M
V0 = 10 mL
[Ca 2+ ]'[Y 4− ]'

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V.2. Titration curve and titration error

V.2.1. Titration curve

pCa V (mL) pCa’

10 0 2.0 initial
9 10.0 … Prior to E.P.
8
19.9 … Prior to E.P.
7
6 20.0 … Equivalence-point (E.P.)
5 21.0 … Beyond E.P.
4 25.0 … Beyond E.P.
3
2
1 V (mL)
0
0 10 20 30

V.2. Titration curve and titration error

V.2.1. Titration curve

- Similar form with acid-base

(a) Titration jump depends on β
titration curve (b) Prior to the E.P., depends on pH
- Having the titration jump (end and auxiliary ligand
point sharpness)
(c) Beyond the E.P., depends on pH

Fe 3+

Hg2+

Zn2+
Fe 2+

Ca2+

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V.2. Titration curve and titration error

V.2.1. Titration curve
V.2.2. Titration error

C0V0
= [Ca 2+ ]'+[CaY 2− ] (1)
V + V0 CV − C0V0 V + V0
q = P −1 = = ([Y ]'−[M ]') (4)
CV C0V0 C0V0
= [Y 4− ]'+[CaY 2− ] (2)
V + V0
[CaY 2− ] 1 CV
β'= (3) [Y 4− ]' = ( 0 0 −[M ]') (5)
[Ca 2+ ]'[Y 4− ]' β '[M ]' V +V0

1 V + V0 (6)
At all point q= −[M ]'
β '[M ]' C0V0

1 C + C0 (7)
Close to the E.P q= −[M ]'
β '[M ]' CC0

V.3. Indicators for EDTA titration

V.3.1. Classification of indicators

- One color indicator: sunfosalicylic acid (Fe3+);

- Redox indicators: ferroin (Fe3+)
- Metal indicators

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V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal indicators

Requirements:

- Compound must be chemically stable throughout the titration

- It should form 1:1 complex weaker than the metal-EDTA complex.

- Color of the ind. and the metal complexed ind. must be sufficiently different.

- The indicator should not compete with the EDTA.

- The transition range (pM range) must be within the titration jump
- Complexes are intensely colored (detected visually at conc. of 10 -6 to 10-7 M)

V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal indicators

Name of the Indicators Color change pH range Metals detected

Eriochrome black T Red to blue 6-7 Ca, Ba, Mg, Zn, Cd,
Mn, Pb, Hg
Murexide Violet to blue 12 Ca, Cu, Co
Cetechol-violet Violet to red 8-10 Mn, Mg, Fe, Co, Pb
Methyl Blue Blue to yellow 4-5 Pb, Zn, Ca, Hg
Alizarin Red to yellow 4-5 Pb, Zn, Co, Mg, Cu
Sodium Alizarin Blue to Red 4 Al, Th
sulphonate
Xylenol orange Lemon to 4-6 Pb, Zn, Cd, Hg
Yellow

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V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal-ion indicators

10-6.3
Eriochrome Black T
10-11.6

Mechanism of action of indicator at the end point of titration, in

case direct titration of M with EDTA

V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal indicators

Example: Determine the transition range for Erio-T

in titrating of Mg2+ and Ca2+ at pH 10.0

Given the K2 (Erio-T) = 10-11.6 and

βMgIn- =107; βCaIn- =105.4 ;

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V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal indicators

6.4

4.8
4.4

2.8

V.3. Indicators for EDTA titration

V.3.1. Classification of indicators
V.2.2. Metal indicators

Example: A titration of 100 mL solution of CaCl2 requires 40.0 mL of

0.0100 M EDTA solution to the end point of Erio-T at pH 10.0. Given
that at the end point, 50% of indicator exits in the complex with metal
ion.
a. Write the reaction during the titration
b. Calculate the titration error
c. Calculate the concentration of CaCl2 with the consideration of
titration error.
Given β’(CaY2-)=10 10.25; β’(CaIn-) 10 3.79; β’(CaIn-)=10 3.8

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V.4. Titration methods involving EDTA

Direct titration Back titration Replacement
titration
React. M + In → MIn M + Yexcess → MY M + MgY2- → MY + Mg2+
Mg2+ + In → MgIn
M + Y → MY Y + Mg2+ → MgY2- Mg2+ + Y → MgY

MIn + Y → MY + In In + Mg2+ → MgIn MgIn + Y → MgY + In

Calc. #mol M = #mol Y #mol M + #mol Mg #mol M = #mol Mg =

= #mol Y #mol Y
Cond. Having suitable ind. β(MY) > β(MgY) β(MY) > β(MgY)
No suitable ind. No suitable ind.
Slow reaction of MY
Ions Mg, Ca, Zn, Cd, Pb Cr, Co, Al (slow Al , Ba
Cu, Co, Ni, Mn, … react)

V.5. Applications of EDTA titrations

• Does not have high selectivity

• Samples with mixture of metal ions,
require separation of ions by
• pH control
• Precipitation
• Extraction
• Masking/demasking

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V.5. Applications of EDTA titrations

• Food additives: prevent oxidation, and maintain

color
• Food analyses: calcium, iron determinations
• Medical application: detoxification in heavy
metals poisoning case, iron therapy
• Drug analyses: iron, cobalt determinations

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6 Precipitation Titrations
VI.1. Introduction to argentometry

VI.2. Titration curves: Case of titration of halide by silver ions

VI.2.1. General equation of titration curve
VI.2.2. Shape of the titration curves
VI.2.3. Effects of reaction completeness
VI.2.4. Titration errors
VI.2.5. Inverse titration
VI.3. End point detection
VI.3.1. Argentometry in acidic medium: Volhard’s method
VI.3.2. Argentometry in neutral or weakly alkaline medium: Mohr’s method
VI.3.3. Argentometry in weakly acidic or neutral medium: Fajans’ method

VI.1. Introduction to argentometry

AgI
AgCN
AgSCN AgBr
AgCl
AgBrO3 AgIO3 pKs

4.2 7.5 9.7 12.0 12.3 14.9 16.1

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VI.2. Titration curves, titration errors

VI.2.1. General equation of titration curve

Direct titration Cl⁻ with Ag+

Ag +
CV
C = 0.10 M
V = mL
CAg+ = = [Ag+ ]+ mAgCl (1)
V +V0
C0V0 (2)
CCl − = = [Cl − ]+ mAgCl
V +V0
K s = [Ag+ ][Cl − ] (3)
Cl⁻
C0 = 0.050 M
V0 = 10 mL

VI.2. Titration curves, titration errors

VI.2.1. General equation of titration curve
VI.2.2. Shape of titration curve

Direct titration Cl⁻ with Ag+

pKs (AgCl) = 9.74;
V (mL) pAg
Ag +
C = 0.10 M 10.0 Prior to E.P.
V = mL
24.0 Prior to E.P.
25.0 (E.P.)
26.0 Beyond E.P.
30.0 Beyond E.P.

Cl⁻
C0 = 0.050 M
V0 = 50 mL

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VI.2. Titration curves, titration errors

VI.2.1. General equation of titration curve
VI.2.2. Shape of titration curve

Direct titration Cl⁻ with Ag+

9

Ag +
C = 0.10 M 7
V = mL

pAg 5

Cl⁻
1
C0 = 0.050 M 0 10 20 30 40 50
V0 = 50 mL V (mL)

VI.2. Titration curves, titration errors

VI.2.1. General equation of titration curve
VI.2.2. Shape of titration curve

Cl = 0.05 M; Ag = 0.1 M

Cl = 0.005 M; Ag = 0.01 M
7

Properties of titration curves:

pAg 5 - Symmetric
- Prior to E.P, depending on C, C0, Ks
- After E.P., depending on C, C0
3

1
0 10 20 30 40 50
V (mL)

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VI.2. Titration curves, titration errors

VI.2.1. General equation of titration curve
VI.2.2. Shape of titration curve
VI.2.3. Effect of reaction completeness

17

15

13

11 I; pKs (AgI) = 16.1

Br, pKs (AgBr) = 12.3

pAg 9
Cl; pKs (AgCl) = 9.7
7
IO3; pKs (AgIO3) = 7.5
5

1
0 10 20 30 40 50
V (mL)

VI.2. Titration curves, titration errors

VI.2.4.Titration errors

CV
CAg+ = = [Ag+ ]+ mAgCl (1)
V +V0 CV − C0V0 V + V0
q = P −1 = = ([Ag+ ]−[Cl − ]) (4)
C0V0 C0V0
CV
CCl − = 0 0 = [Cl − ]+ mAgCl (2)
V +V0
K s = [Ag+ ][Cl − ] (3)

K s V + V0
At all point q = ([Ag+ ]− ) (5)
[Ag+ ] C0V0

K s C + C0
Close to the E.P q = ([Ag+ ]− ) (6)
[Ag+ ] CC0

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VI.2. Titration curves, titration errors

VI.2.4.Titration errors

Ag + Exercise 1:
0.010 M Titration of 100.0 mL of 0.0050 M KI with a solution of 0.01 M AgNO3
a) Calculate pAg at 45.00; 49.50; 50.50; 55.00 mL
b) Calculate the titration jump within error of ± 0.1%.

I⁻
0.0050 M
100 mL

VI.2. Titration curves, titration errors

VI.2.5. Inverse titration

Use in BACK titration

pAg Determinations of PO43-;
17
AsO43-; and CrO42-
CN -
C = 0.10 M 13
V = mL K s V +V0
P −1 = −([Ag+ ]− )
9
[Ag+ ] C0V0

K s C + C0
5 q = −([Ag+ ]− )
[Ag+ ] CC0

1
0 10 20 30 40 50
Ag +
V (mL)
C0 = 0.050 M
V0 = 50 mL

5
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VI.3. End-point detection

VI.3.1. Argentometry in acidic medium: Volhard’s method

SCN- Titration reaction: SCN- + Ag+ → AgSCN (s, white)

End point: SCN- + Fe3+→ FeSCN2- (aq, red)

Sensitivity FeSCN2- 6 × 10 -6 M

Does the formation of the colored complex

close to the E.P. distort the titration?

Using in BACK titration, when determining Cl-,

Ag+ removing AgCl before titration is necessary. Why?
Ind. Fe3+
Medium H+
pK s (AgCl) = 10; pK s (AgSCN) = 12; lgβ (FeSCN 2-) = 3.03

VI.3. End-point detection

VI.3.1. Argentometry in acidic medium: Volhard’s method

SCN- Titration reaction: SCN- + Ag+ → AgSCN (s, white)

End point: SCN- + Fe3+→ FeSCN2+ (aq, red)

Calculate the titration error of the titration of 0.020 M Ag+

with the 0.010 M SCN-.
Considering that at the end point
[FeSCN2- ] = 6 × 10 -6 M; [Fe3+] = 5 × 10 -3 M

Ag+
Ind. Fe3+
Medium H+
pK s (AgSCN) = 12; lgβ (FeSCN 2+) = 3.03

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VI.3. End-point detection

VI.3.1. Argentometry in acidic medium: Volhard’s method
VI.3.2. Argentometry in neutral or weakly alkaline medium: Mohr’s method

Titration reaction: Ag+ + Cl- → AgCl (s, white)

Ag+ 0.1 M End point: 2Ag+ + CrO42- → Ag2CrO4 (s, red)

Mechanism of the endpoint indication: Titration error

Calculate the theoretical concentration of CrO42- must

be exist in order to obtain a perfect titration (end point
meets the E.P)?

The practical conc. Is used of 5 × 10 -3 M. Calculate the

Cl- 0.1 M titration error?
Ind. CrO42-
Neutral/weakly alkaline
pK s (AgCl) = 10; pK s (Ag2 CrO4 ) = 11.89

VI.3. End-point detection

VI.3.1. Argentometry in acidic medium: Volhard’s method
VI.3.2. Argentometry in neutral or weakly alkaline medium: Mohr’s method

Ag+ 0.1 M pH Conditions

6.5 < pH < 10.5 pH

[CrO42-] decrease Ag2O formation

2CrO42- + 2H+ ! 2HCrO4-

2HCrO4- ! Cr2O72- + H2O 2Ag+ + 2OH- ! Ag2O + H2O
Cl- 0.1 M
Ind. CrO42-
Neutral/weakly alkaline

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VI.3. End-point detection

VI.3.1. Argentometry in acidic medium: Volhard’s method
VI.3.2. Argentometry in neutral or weakly alkaline medium: Mohr’s method

Ag+
0.060 M Exercise 2:
Titration of 50.00 mL KBr requires 25.00 mL of 0.060 M
AgNO3 with 0.0030 M K2CrO4 as indicator. Calculate a KBr
concentration and titration error.

Br-
Ind. CrO42- 0.003 M

pK s (AgBr) = 12; pK s (Ag2 CrO4 ) = 11.89

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7 Redox Titrations
VII.1. Introduction to redox titrations

VII.2. Titration curves and titration errors

VII.2.1. Titration of ferrous ions by the ceric ions
VII.2.2. Titration of stannic ions by the chromous ions

VII.3. Indicators

VII.4. Redox titrimetric methods

VII.4.1. Manganimetry
VII.4.2. Iodometry
VII.4.3. Chromimetry

VII.1. Introduction to redox titration

S Thermodynamic condition: a titration reaction must be as complete

as possible
S ΔE° > 0.24 V: 1% of the species remains to be titrated at the E.P
S ΔE° > 0.36 V: 0.1% of the species remains to be titrated at the E.P

S Kinetic conditions: a titration reaction must be as fast as possible.

S The rate depends on the mixture’s composition
S The rate depends on the reaction mechanism
S The rate may be considerably increased with the use of catalysts

1
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VII.2. Titration curves, titration errors

VII.2.1. Titration of the ferrous ions by the ceric ions

Fe2+ + Ce (IV) ! Ce (III) + Fe3+ K = 10 12.8

[Fe3+ ]'
E = E o'Fe3+ /Fe2+ + 0.0592 lg (1)
Ce4+ [Fe 2+ ]'
C = 0.10 M [Ce 4+ ]'
V = mL
o'
E = E Ce 4+ + 0.0592 lg (2)
/Ce3+
[Ce3+ ]'
C0V0 (3)
[Fe3+ ]'+[Fe 2+ ]' = =X
V +V0
CV (4)
[Ce 4+ ]'+[Ce3+ ]' = =Y
V +V0
[Fe3+ ]' = [Ce3+ ]' (5)
Fe2+ , H 2 SO 4 1M
C0 = 0.10 M
V0 = 50 mL E o'Fe3+ /Fe2+ = 0.68 V; E Ce
o'
= 1.44 V
4+
/Ce3+

VII.2. Titration curves, titration errors

VII.2.1. Titration of the ferrous ion by the ceric ion

Fe2+ + Ce (IV) ! Ce (III) + Fe3+ K = 10 12.8

0.0592 P
Ce4+ Before the E.P. E = E o'Fe3+ /Fe2+ + lg
C = 0.10 M 1 1− P
V = mL
1+ q
E = E o'Fe3+ /Fe2+ + 0.0592 lg
−q
o' 0.0592
After the E.P. E = E Ce 4+
/Ce3+
+ lg(P −1)
1
o'
E = E Ce 4+
/Ce3+
+ 0.0592 lg q

E o'Fe3+ /Fe2+ + E Ce
o'
4+
/Ce3+
At the E.P. Ee. p. =
Fe2+ , H 2 SO 4 1M 1+1
C0 = 0.10 M
V0 = 50 mL
E o'Fe3+ /Fe2+ = 0.68 V; E Ce
o'
4+
/Ce3+
= 1.44 V

2
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VII.2. Titration curves, titration errors

VII.2.1. Titration of the ferrous ion by the ceric ion

Fe2+ + Ce (IV) ! Ce (III) + Fe3+ K = 10 12.8

P = 0.5

P =1

P=2

VII.2. Titration curves, titration errors

VII.2.1. Titration of the ferrous ion by the ceric ion

Fe2+ + Ce (IV) ! Ce (III) + Fe3+ K = 10 12.8 1.5

E

1.44
1.3
o'
P = 0.5 E = E Fe3+ /Fe2+
= 0.68
o' o'
E Fe3+ /Fe2+
+ E Ce 4+
/Ce3+
1.1
1.06
P =1 E= = 1.06
2
o' 0.9
P=2 E = E Ce4+ /Ce3+ = 1.44

0.7
0.68
P=0.5 P=1 P=2
Symmetric titrations: n1 = n2 0.5
Not depend on C, C 0 0 12.5 25 37.5 50
V (mL)

3
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VII.2. Titration curves, titration errors

VII.2.1. Titration of the ferrous ion by the ceric ion

Fe2+ + Ce (IV) ! Ce (III) + Fe3+ K = 10 12.8 1.5

E

1.44
1.3
Calculate the titration jump with the
error in range of ± 0.1%
1.1
1.06

0.9

0.7
0.68
P=0.5 P=1 P=2
0.5
0 12.5 25 37.5 50
V (mL)
E o'Fe3+ /Fe2+ = 0.68 V; E Ce
o'
4+
/Ce3+
= 1.44 V

VII.2. Titration curves, titration errors Cr 2+

C = 0.10 M
VII.2.1. Titration of the ferrous ions by the ceric ions V = mL

VII.2.2. Titration of the stannic ions by the chromous ions

2Cr2+ + Sn4+ ! 2Cr3+ + Sn2+ K = 10 17.6 E Sn4+

C0 = 0.10 M
0.14 V0 = 25 mL
o' 0.0592 P 0.15
E=E Sn 4+ /Sn 2+
− lg
2 1− P

o' 0.0592 -0.05

-0.03
E = E Cr 3+
/Cr 2+
− lg(P −1)
1

2E o'Sn4+ /Sn2+ +1E Cr

o'
3+
/Cr 2+
Ee. p. = -0.25
2 +1
-0.38
Asymmetric titrations: n1 ≠ n2
Not depend on C, C 0 P=0.5 P=1 P=2
-0.45
0 25 50 75 100
E o'Sn4+ /Sn2+ = 0.14 V; E Cr
o'
3+
/Cr 2+
= −0.38 V V (mL)

4
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VII.3. Indicators

ü Internal redox indicators, e.g. ferroin,(complex of Fe(II) with 1,10-

phenanthroline), diphenylamine, phenothiazine, and diphenylpyrazine;

ü Special redox species are purely and simply one (or several) of the reactants
of the redox titration under consideration. They also play the role of indicators.
For example, it is the case with iodine–iodide and of potassium permanganate
solutions;

ü Specific indicators exhibit a particular color in the presence of a given

reactant or product. It is the case for a starch solution in the presence of iodine
and iodide

VII.3. Indicators
VII.3.1. Internal redox indicators

[Inox ]'
E = E o'In + 0.0592 lg
[Inred ]'

1 [Inox ]'
< < 10
10 [Inred ]'
0.0592 0.0592
EIno' − < interval change < EIno' +
n n

5
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VII.3. Indicators
VII.3.1. Internal redox indicators

Ferroin Eo’ =1.06 V (1 M HCl)

Echange = …….. V

VII.3. Redox titration methods

VII.4.1. Manganimetry
VII.4.2. Iodometry
VII.4.3. Chromimetry

Manganimetry Iodometry Chromimetry

Titration Red + MnO 4 − ! Ox + Mn2+ Red +I 3 − ! Ox + I− Fe2+ + Cr2 O 7 2- ! Fe3+ + Cr3+
reactions (direct titration: Fe2+, H 2 C2 O 4 , (Vit.C, Sn2+, CN −, …)
NO 2 −, H 2 O 2 )

Red + Fe3+ ! Ox + Fe2+ Ox + I − ! Red +I 3 − Red + Fe3+ ! Ox + Fe2+

Fe2++ MnO 4 − ! Fe3+ + Mn2+ I 3 − + S2 O 3 2− ! 3I− + S4O 62− Fe2++ Cr2 O 7 2- ! Fe3+ + Cr3+
(rep. titration, NH 2 OH, Cr2+) (Cu2+, Fe3+, H 2 O 2 , …)

Ox + Fe2+ ! Red + Fe3+ Red +I 3 − ! Ox + I− Ox + Fe2+ ! Red + Fe3+

Fe2++ MnO 4 − ! Fe3+ + Mn2+ I 3 − + S2 O 3 2− ! 3I− + S4O 62− (Red + Cr2 O 7 2- ! Ox+ Cr3+)
(back titration: S2 O 8 2−,MnO 2 , …) (SCN −, CN − Fe2++ Cr2 O 7 2- ! Fe3+ + Cr3+

Indicator Internal indicator Starch Diphenylamine

Medium Strong acidic Slightly acidic 2 < pH < 5 Strong acid
Standard KMnO4 , standardized with Na2 S2 O3 , standardized with K2 Cr2 O7
solution H2 C 2 O4 K2 Cr2 O7