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Titration

2 MnO4- + 5 H2C2O4 + 6 H+
(purple)
(colorless)

Lecture # 8

10 CO2 + 2 Mn2+ + 8 H2O


(colorless) (colorless)

Volumetric Analysis
10

0 mL
Titrate
(solution)

Titrations in Analytical Chemistry

11

Analyte
(solution)

Other Forms of Titration

Gravimetric
Analysis

End Point vs. Equivalence Point

e.g. Titer Plates


Enzyme-Linked
Immunosorbent Assay
(ELISA)

Titrate
(solution)

Equivalence Point
occurs when the quantity of
added titrant is the exact
amount necessary for
stoichiometric reaction with the
analyte
End Point > Equivalence Point
(titration error)
Analyte
(solution)

Minimizing Titration Error


1. Blank Titration

End Point

Minimizing Titration Error


1. Blank Titration
2. Back Titration

Titrate
(solution)

Blank
(No Analyte)

Back Titration
Direct
Titration

Minimizing Titration Error

Back
Titration

1. Blank Titration
2. Back Titration
3. Choose a property that is easily observable!

Titrate
(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
(Electrochemistry)

Excess
Titrant
Analyte
(solution)

Spectrophotometric Titration
=

total volume x Observed


initial volume Absorbance

End Point

Volume of Titrant Added

Absorbance

Absorbance

Corrected
Absobance

Spectrophotometric Titration

Concentration

Titration Calculations
2 KMnO4 + 5 H2O2 + 3 H2SO4

0.040 M
KMnO4

2 MnSO4 + K2SO4 + 5 O2 + 8 H2O

Primary Standard: pure enough to be weighed


and used directly

Standard Solution = 0.040 M KMnO4


26.32 mL of KMnO4 added
What is the molar concentration of H2O2?

H2O 2
+ H2SO4
(25 mL)

Purity of Titrant

0.040 mol/L x 0.02632 mL = 0.001 mol KMnO4


Moles of H2O2 = 5 mol H2O2 x (0.001 mol KMnO4)
2 mol KMnO4
= 0.005 mol H2O2
Molar Concentration = 0.005 mol/(0.025 L) = 0. 2 M

Technical Grade
Primary
Standard

ACS Reagent Grade


Ultra Pure

Trace Analysis (11000 ppm)


Ultratrace Analysis
(<1 ppm)

Standardization
prepare titrant with approximately the desired
concentration and use it to titrate a primary standard

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+
(purple)
(colorless)

10 CO2 + 2 Mn2+ + 8 H2O


(colorless) (colorless)

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

Johan Kjeldahl
(1849-1900)

(2 mol MnO4- / 5 mol C2O42-) x 0.003731 mol C2O42= 0.001492 mol MnO4

0.001492 mol /0.03907 L = 0.03819 M MnO4-

Kjeldahl Digestion

Kjeldahl Digestion (continued)


NH3 + HCl (excess)
HCl + NaOH

NH4+ + Cl- + HCl


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
H2SO4 (+ K2SO4)
(Sample)
338C
NaOH + NH4+ NH3 (g) + H2O

(0.00326 L)(0.02 mol/L NaOH) = 0.0000652 mol NaOH


0.0002 - 0.0000625 = 0.0001375 mol NH3
= 0.0001375 mol N
0.0001375 mol x (14.00674 g/mol) = 0.00193 g N/g grain

Steam Distillation to Collect NH3

Fajans Titration

AgCl (s) + Ag+

Filter and Wash

Ag+ + K+SCN- + Fe3+


(filtrate)

AgSCN (s) + FeSCN2+


(end point)

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

+ -

+ -

Ag+ + H+ + NO3- + Cl-

After Equivalance Point

Before Equivalance Point

Volhard Titration

+ -

The Titration Curve

Fajans Titration

a graph showing how the concentration of one of


the reactants varies as titrant is added.

Dichlorofluorescein

p-function:

The Titration Curve

The Titration Curve

a graph showing how the concentration of one of


the reactants varies as titrant is added.
Ag+ + I-

AgI (s)

Ksp = 1.2 x

1016

AgI (s)

pX = - log [X]

Ag+ + I-

Ksp = 8.3 x

10-17

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

a graph showing how the concentration of one of


the reactants varies as titrant is added.
Ag+ + I-

AgI (s)

Ksp = 1.2 x

1016

AgI (s)

Ag+ + I-

Ksp = 8.3 x 10-17

Before equivalence point:


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


the reactants varies as titrant is added.
Ag+ + I-

AgI (s)

Ksp = 1.2 x 1016

AgI (s)

Ag+ + I-

Ksp = 8.3 x 10-17

At the equivalence point:


e.g. 50.00 mL of Ag+ added. What is [Ag+]?
[Ag+] = [I-] = x

8.3 x 1017

Ag+ + I-

AgI (s)

Ksp = 1.2 x 1016

AgI (s)

Ag+ + I-

Ksp = 8.3 x 10-17

After the equivalence point:


e.g. 52.00 mL of Ag+ added. What is [Ag+]?
VAg+ = 52.00 mL - 50.00 mL = 2.00 mL

[Ag+][I-] = (x)(x) = x2 = Ksp = 8.3 x 10-17


x=

a graph showing how the concentration of one of


the reactants varies as titrant is added.

= 9.1 x 10-9

pAg+ = - log (9.1 x 10-9) = 8.04

Moles of Ag+ = (0.00200 L)(0.05000 mol/L) = 0.000100 mol


[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 (1.30 x 10-3 ) = 2.89

Titration Curve

Titration Curve

A+ + B-

A+ + B-

Before Equivalence
Point

[I-] =

AB (s)

[B-] =

Ve VA+
Ve

[B-]i

VBVB- + VA+

After Equivalence
Point

AB (s)

[A+] =

VA+ Ve [A+]
i
VB- + VA+

[A+] = 52.00 mL 50.00 mL (0.050 M)


25.00 mL + 52.00 mL

50.00 mL 10.00 mL
25.00 mL
(0.100 M)
50.00 mL
25.00 mL + 10.00 mL

= (2/77)(0.050 M) = 1.30 x 10-3 M

= (4/5)(0.100 M)(25/35) = 0.05714 M

pA+ = - log [A+]

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

pAg+ = -log (1.30 x 10-3) = 2.89

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

The Titration Curve

The Titration Curve


14

12

12

10
Equivalance Point

pA+

pAg+

A
14

6
4

2
30

40 50 60
VAg+ (mL)

70

80

>

AB

[B-]

> [B-]C

4
20

[B-]

10

10

A+ + B-

C
B
A
10

20

30

40 50 60
VA+ (mL)

70

80

The Titration Curve


B
14

pA+

12

A+ + B-

AB

A+ + C-

AC

A+ + D-

AD

10

4
2
10

20

30

40 50 60
VA+ (mL)

70

80