Titration

2 MnO4- + 5 H2C2O4 + 6 H+ 10 CO2 + 2 Mn2+ + 8 H2O

(purple) (colorless) (colorless) (colorless)
Lecture # 8 Volumetric Analysis
10
0 mL

Titrate
(solution)
Titrations in Analytical Chemistry 11

Analyte
(solution)
Gravimetric
Analysis

Other Forms of Titration End Point vs. Equivalence Point

e.g. Titer Plates

Enzyme-Linked Equivalence Point

Titrate occurs when the quantity of
Immunosorbent Assay
(ELISA) (solution) added titrant is the exact
amount necessary for
stoichiometric reaction with the
analyte

End Point > Equivalence Point

(titration error)

Analyte
End Point
(solution)

Minimizing Titration Error Minimizing Titration Error

1. Blank Titration 1. Blank Titration

2. Back Titration
Titrate
(solution)

Blank
(No Analyte)

1
 Back Titration Minimizing Titration Error
Direct Back
Titration Titration 1. Blank Titration
2. Back Titration
Titrate 3. Choose a property that is easily observable!
(solution)
1. Observing Color Change of an Indicator
2. Precipitation/Dissolution
3. Detection of Color Change (Absorption of
Light = Spectrophotometry)
4. Detection of Change in Voltage or Current
Excess (Electrochemistry)
Titrant
Analyte
(solution)

Spectrophotometric Titration Spectrophotometric Titration

Corrected = total volume x Observed
Absobance initial volume Absorbance
Absorbance

Absorbance

End Point

Volume of Titrant Added Concentration

Titration Calculations Purity of Titrant

2 KMnO4 + 5 H2O2 + 3 H2SO4 2 MnSO4 + K2SO4 + 5 O2 + 8 H2O
Primary Standard: pure enough to be weighed
and used directly
Standard Solution = 0.040 M KMnO4
0.040 M Technical Grade
KMnO4
26.32 mL of KMnO4 added ACS Reagent Grade
Primary
Standard
What is the molar concentration of H2O2? Ultra Pure Trace Analysis (1-
1000 ppm)
0.040 mol/L x 0.02632 mL = 0.001 mol KMnO4
Ultratrace Analysis
H2O 2 (<1 ppm)
Moles of H2O2 = 5 mol H2O2 x (0.001 mol KMnO4)
+ H2SO4 2 mol KMnO4 Standardization
(25 mL) prepare titrant with approximately the desired
= 0.005 mol H2O2
concentration and use it to titrate a primary standard
Molar Concentration = 0.005 mol/(0.025 L) = 0. 2 M

2
 Standardization Kjeldahl Digestion
Example:We make an approximately 0.04 M solution of
KMnO4. We dissolve 500.00 mg of a primary standard
of sodium oxalate in 250.0 mL of water, and use this to
standardize. A volume of 39.07 mL is required to titrate
the standard solution. What is the actual concentration
of MnO4-?
2 MnO4- + 5 H2C2O4 + 6 H+ 10 CO2 + 2 Mn2+ + 8 H2O
(purple) (colorless) (colorless) (colorless)

(0.50000 g/(134.00 g/mol) = 0.003731 mol C2O42-

Johan Kjeldahl
(2 mol MnO4- / 5 mol C2O42-) x 0.003731 mol C2O42- (1849-1900)
= 0.001492 mol MnO4 -

0.001492 mol /0.03907 L = 0.03819 M MnO4-

Kjeldahl Digestion
Kjeldahl Digestion (continued)
NH3 + HCl (excess) NH4+ + Cl- + HCl

HCl + NaOH Na+ + Cl- + H2O

(titration)
Example: Johan Kjeldahl digest 1 gram of grain by his Kjeldahl
Method. He distills the resulting NH3 (following addition of base) into
10 mL of 0.020 M HCl. The unreacted HCl requires 3.26 mL of 0.020
M NaOH. What is the concentration of nitrogen in the gram of grain?
(0.010 L)(0.02 mol/L HCl) = 0.0002 mol HCl (in receiver)
Organic C, H, N NH4+ + CO2 + H2O
(Sample) H2SO4 (+ K2SO4) (0.00326 L)(0.02 mol/L NaOH) = 0.0000652 mol NaOH
338C 0.0002 - 0.0000625 = 0.0001375 mol NH3
NaOH + NH4+ NH3 (g) + H2O = 0.0001375 mol N
Steam Distillation to Collect NH3 0.0001375 mol x (14.00674 g/mol) = 0.00193 g N/g grain

Volhard Titration Fajans Titration

Before Equivalance Point After Equivalance Point
-
Ag+ + H+ + NO3- + Cl- AgCl (s) + Ag+ - - - + + +
-

- + - + - + - + - + - + - +
Filter and Wash
- + - + - + - + - + - + - +
Ag+ + K+SCN- + Fe3+ AgSCN (s) + FeSCN2+ - + - + - + - + - + - + - +
(filtrate) (end point)
- + - + - + - + - + - + - +
-

- + - + - + - + - + - + - +
Ag+ (initial) Ag+ (filtrate) = Ag+ (precipitated with Cl-) - + - + - + - + - + - + - +
- - - + + + -
-

3
 Fajans Titration The Titration Curve
a graph showing how the concentration of one of
Dichlorofluorescein the reactants varies as titrant is added.

p-function: pX = - log [X]

The Titration Curve The Titration Curve

a graph showing how the concentration of one of a graph showing how the concentration of one of
the reactants varies as titrant is added. the reactants varies as titrant is added.

Ag+ + I- AgI (s) AgI (s) Ag+ + I- Ag+ + I- AgI (s) AgI (s) Ag+ + I-

Ksp = 1.2 x 1016 Ksp = 8.3 x 10-17 Ksp = 1.2 x 1016 Ksp = 8.3 x 10-17

Before equivalence point:

25.00 mL of 0.1000 M I- titrated with 0.05000 M Ag+
Ve = Volume added at end point
(0.02500 mL)(0.1000 mol/L) = Ve (0.05000 mol L)
Ve = 0.05000 L = 50.00 mL
e.g. 10.00 mL of Ag+ added. What is [Ag+]?
Moles of I- = (0.02500 L)(0.1000 mol/L) - (0.01000 L)(0.05000 mol/L)
= 0.0025 mol - 0.00050 mol = 0.00200 mol
[I-] = (0.00200 mole)/(0.02500 L + 0.01000 L) = 0.05714 M
[Ag+] = Ksp/([I-] = 8.3 x 10-17 /(0.05714) = 1.45 x 10-15
pAg+ = - log (1.45 x 10-15) = 14.84

The Titration Curve The Titration Curve

a graph showing how the concentration of one of a graph showing how the concentration of one of
the reactants varies as titrant is added. the reactants varies as titrant is added.

Ag+ + I- AgI (s) AgI (s) Ag+ + I- Ag+ + I- AgI (s) AgI (s) Ag+ + I-

Ksp = 1.2 x 1016 Ksp = 8.3 x 10-17 Ksp = 1.2 x 1016 Ksp = 8.3 x 10-17

At the equivalence point: After the equivalence point:

e.g. 50.00 mL of Ag+ added. What is [Ag+]? e.g. 52.00 mL of Ag+ added. What is [Ag+]?
[Ag+] = [I-] = x VAg+ = 52.00 mL - 50.00 mL = 2.00 mL
[Ag+][I-] = (x)(x) = x2 = Ksp = 8.3 x 10-17 Moles of Ag+ = (0.00200 L)(0.05000 mol/L) = 0.000100 mol
x= 8.3 x 1017 = 9.1 x 10-9 [Ag+] = (0.000100 mol)(0.02500 L + 0.05000 L + 0.00200 L)
= (0.000100 mol)/(0.07700 L) = 1.30 x 10-3 M
pAg+ = - log (9.1 x 10-9) = 8.04
pAg+ = - log (1.30 x 10-3 ) = 2.89

4
 Titration Curve Titration Curve
A+ + B- AB (s) A+ + B- AB (s)

Before Equivalence Ve VA+ VB- After Equivalence VA+ Ve [A+]

[B-] = [B-]i [A+] = i
Point Ve VB- + VA+ Point VB- + VA+

[I-] =
50.00 mL 10.00 mL
(0.100 M)
25.00 mL [A+] = 52.00 mL 50.00 mL (0.050 M)
50.00 mL 25.00 mL + 10.00 mL 25.00 mL + 52.00 mL

= (4/5)(0.100 M)(25/35) = 0.05714 M = (2/77)(0.050 M) = 1.30 x 10-3 M

pA+ = - log (Ksp/[B-]) pA+ = - log [A+]

pAg+ = -log (8.3 x 10-17 /0.05714) = 14.84 pAg+ = -log (1.30 x 10-3) = 2.89

The Titration Curve The Titration Curve

A
14 14 A+ + B- AB
B
12 12 [B-] > [B-] > [B-]C
C A B
10 10
pAg+

pA+

8 Equivalance Point 8
6 6 C
4 4 B
A
2 2
10 20 30 40 50 60 70 80 10 20 30 40 50 60 70 80
VAg+ (mL) VA+ (mL)

The Titration Curve

A+ + B- AB
B
A+ + C- AC
14
D A+ + D- AD
12
D
10 B
pA+

8 C
D
6
4
2
10 20 30 40 50 60 70 80
VA+ (mL)