6-1

Chapter 6 Good Titrations

6-1 Principles of Volumetric Analysis
Titration: incremental addition of the titrant to the analyte until completion
buret
fast and complete reactions: acid-base, red-ox, complex, precipitation
HO C
O
C
O
OH 5
+ 2 MnO
4

+ 6 H
+
10 CO
2
+ 2 Mn
2+
+ 8 H
2
O
Analyte Titrant
Oxalic acid Permanganate
(colorless) purple (colorless) (colorless)
Equivalence Point
End Point; actually measured.
marked by a sudden change of physical property of the solution
Indicator, Electrode, Absorbance, Scattering, ...
Titration Error = |End Point - Equivalence Point| Blank titration
Primary standard
Na
2
CO
3
vs. NaOH
Standardization, Standard solution
Direct titration
analyte + titrant product
Back titration; for a clearer end point, to complete the reaction
analyte + reagent 1 product + excess reagent 1
product excess reagent 1 + reagent 2
6-2 Titration Calculations
Relate the moles of titrant to the moles of analyte
1:1 Stoichiometry
C
1
V
1
= C
2
V
2
Ex 10.00 mL chloride solution requires 22.97 mL of 0.05274 M AgNO
3
Ag
+
(aq) + Cl

(aq) AgCl(s) K = 1/K

SP
= 5.6 10
9
[Cl

] = 22.97 mL 0.05274 M / 10.00 mL = 0.1211

4
M
6-2
x:y Stoichiometry
CV
n
C V
n
1 1
1
2 2
2
= n
1
A + n
2
B product
Ex Titration of H
2
C
2
O
4
with MnO
4

10.00 mL of unknown oxalic acid solution requires 15.44 mL of 0.01117 M KMnO

4
10.00 mL of blank solution requires 0.04 mL of 0.01117 M KMnO
4
5 H
2
C
2
O
4
+ 2 MnO
4

+ 6 H
+
10 CO
2
+ 2 Mn
2+
+ 8 H
2
O
[C
2
O
4
2
] = (5/2) 0.01117 M (15.44 0.04) mL / 10.00 mL = 4.300 10
2
M
Standardization of Titrant Followed by Analysis of Unknown
Determination of the Calcium Content in Urine
1. Ca
2+
precipitated with excess oxalate in basic solution
Ca
2+
(aq) + C
2
O
4
2
(aq) Ca(C
2
O
4
)H
2
O(s)
2. Wash with ice-cold water to remove excess oxalate
3. Ca(C
2
O
4
)H
2
O(s)
excess hot H
+
Ca
2+
(aq) + H
2
C
2
O
4
(aq)
mol of H
2
C
2
O
4
= mol of unknown Ca
2+
4. Titration with permanganate in acidic solution
9095% at 25C then at 60C: Fowler and Bright method (1935)
5 H
2
C
2
O
4
+ 2 MnO
4

+ 6 H
+
10 CO
2
+ 2 Mn
2+
+ 8 H
2
O
* KMnO
4
solution is standardized against primary standard Na
2
C
2
O
4
A Back Titration
Ex 25.00 mL of cyanide solution was treated with 20.00 mL of 0.03856 M Ni
2+
4 CN

+ Ni
2+
Ni(CN)
4
2
The excess Ni
2+
back-titrated with 11.77 mL of 0.02307 M EDTA
Ni
2+
+ EDTA
4
Ni(EDTA)
2
mol of the initial Ni
2+
= (0.02000 L) (0.03856 M) = 7.712
0
10
4
mol
mol of the excess Ni
2+
= (0.01177 L) (0.02307 M) = 2.715
3
10
4
mol
mol CN

= (7.712
0
10
4
2.715
3
10
4
) 4 = 1.998
7
10
3
mol
[CN

] = 1.998
7
10
3
mol / 0.02500 L = 0.07995 M
EDTA (ethylenediaminetetraacetic acid) back titration (p. 278)
If the analyte precipitates in the absence of EDTA
If the complexing is too slow
If blocking of the indicator; Cu
2+
, Ni
2+
, Co
2+
, Cr
3+
, Fe
3+
, Al
3+
Metal ion indicator: MgIn + EDTA MgEDTA + In
N
N
COO

COO

COO

COO

6-3
6-3 Titration of a Mixture
Ag
+
+ Cl

AgCl(s) K
sp
(AgCl) = 1.8 10
10
Ag
+
+ I

AgI(s) K
sp
(AgI) = 8.3 10
17
The less soluble precipitate will be formed first.
K
sp
(AgI) << K
sp
(AgCl)
Qualitative Picture of Fig 6-4 (cf. Fig 14-2)
1) AgI(s) precipitates and [Ag
+
] remains low.
2) When the l

is consumed, [Ag
+
] abruptly increases.
3) AgCl(s) begins to precipitate.
4) When the Cl

is consumed, [Ag
+
] abruptly increases.
5) Shortly after the equivalence point for AgCl, [Ag
+
] levels off.
V
Ag+
pAg
+
(1)
(2)
(3)
(4)
(5)
23.85 mL vs. 23.76 mL
Coprecipitation of AgCl with AgI
Random error
6-4 Chemistry in a Fishtank
oxoanions per largest ClO
4

perchlorate
ate larger number of oxygens ClO
3

chlorate
ite smaller number of oxygens ClO
2

chlorite
hypo smallest ClO

hypochlorite
6-4
higher
plants
amino
acids
higher
animals
urea NH
3
nitrifying
bacteria
(Nitrobacter)
nitrifying
bacteria
(Nitrosomonas)
Nitrogen Cycle
NO
2

nitrite
NO
3

nitrate
N
2
in air
nitrogen-
fixing
bacteria
Box 6-1 Studying Marine Ecosystem
Need to measure [NO
2

] Need standard solution of NaNO

2
Step 1 Mix a stock solution of NaNO
2
with excess KMnO
4
standard solution.
5 NO
2

+ 2 MnO
4

+ 6 H
+
5 NO
3

+ 2 Mn
2+
+ 2 H
2
O
(slow reaction, unstable NO
2

)
Step 2 Add Na
2
C
2
O
4
standard solution in 10.00-mL aliquots until the purple disappears.
excess H
2
C
2
O
4
Step 3 Back-titrate the excess H
2
C
2
O
4
in the warm solution with standard KMnO
4
Step 4 Blank titration
Ex Step 1: 50.00 mL of 0.01054 M KMnO
4
, 5 mL of H
2
SO
4
, 50.00 mL of NaNO
2
Step 2: Add two 10.00-mL aliquots of 0.02500 M Na
2
C
2
O
4
to use up MnO
4

.
Step 3: 2.11 mL of 0.01054 M KMnO
4
for back titration of the excess H
2
C
2
O
4
Step 4: 0.06 mL of 0.01054 M KMnO
4
for blank titration
Solution Strategy
total moles of KMnO
4
used the moles that reacted with Na
2
C
2
O
4
total vol of KMnO
4
= 50.00 (step 1) + 2.05 (steps 3 &4) = 52.05 mL
total mol of KMnO
4
= 0.05205 L 0.01054 M = 5.486
0
10
4
mol
vol of Na
2
C
2
O
4
= 20.00 mL
mol of Na
2
C
2
O
4
= 0.02000 L 0.02500 M = 5.000
0
10
4
mol
mol of KMnO
4
reacted with Na
2
C
2
O
4
=
2
5
5.000
0
10
4
= 2.000
0
10
4
mol
mol of KMnO
4
reacted with NaNO
2
= (5.486
0
2.000
0
) 10
4
= 3.486
0
10
4
mol
[NaNO
2
] = 3.486
0
10
4
mol
5
2
0.05000 L = 0.01743 M
6-5
6-5 Titrations involving Silver Ion
Argentometric titrations: titration with Ag
+
Mohr Titration
First appearance of red Ag
2
CrO
4
titration reaction: Ag
+
+ Cl

AgCl(s)
end-point reaction: 2 Ag
+
+ CrO
4
2
Ag
2
CrO
4
(s)
The pH should be in the range of 410.5.
Blank titration or standardization of AgNO
3
is needed.
Good for Cl

and Br

Volhard Titration
Back titration of the excess Ag
+
1) Cl

is precipitated by a known, excess quantity of standard AgNO

3
Ag
+
+ Cl

AgCl(s)
2) AgCl isolated by filtering or adding nitrobenzene. (not needed for Br

and I

)
Otherwise, AgCl is replaced by AgSCN.
3) Excess Ag
+
is back titrated with KSCN in the presence of acidic Fe
3+
Ag
+
+ SCN

AgSCN(s)
Fe
3+
+ SCN

FeSCN
2+
Useful for the determination of any anions that forms an insoluble silver salt.
Fajans Titration
Adsorption indicator
Fig 6-6 Ag
+
is added to Cl

1) Before the equivalence point: excess Cl

, negative charge on the crystal surface

2) After the equivalence point: excess Ag
+
, positive charge on the crystal surface
3) Anionic dyes are adsorbed on the positively charged crystal surface.
pH > pK
a
of dyes
Large surface area: dextrin, low electrolyte concentration
Avoid photodissociation
Color Plate 2
Tab 6-1 Applications of Precipitation Titrations
Fajans method has wider application.
Homework
AY6-B, AY6-E, 5, 6, 8, 10, 14