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Chem 28 Post Lab 2
Chem 28 Post Lab 2
Methods
Titrations
- widely used in analytical chemistry to determine acids,
bases, oxidants, reductants, metal ions, proteins, and
many other species.
Titration methods (titrimetric methods)
-include a large and powerful group of quantitative
procedures based on measuring the amount of a reagent
of known concentration that is consumed by an analyte
in a chemical or electrochemical reaction.
- concentration of the unknown can be calculated using
the stoichiometry of the reaction and the number of
moles of standard solution required to reach the end
point
Titrimetric methods
-Widely used for routine determination because they are rapid, convenient,
accurate, and readily automated
Types
Volumetric Titrimetry
-Involves measuring the the volume of a solution of known concentration that
is required to react essentially completely with the analyte
Gravimetric Titrimetry
-Mass of the reagent is measured instead of its volume
Coulometric Titimetry
-The reagent is a constant direct electrical current of known magnitude that
consumes the analyte
- the time needed to complete the electrochemical reaction is measured
PRECIPITATION TITRATION
-Based upon reactions that yield ionic compounds of limited
solubility
- one of the oldest analytical techniques dating to the mid-1800s
-The slow rate of formation of most precipitates, however, limits
the number of precipitating agents that can be used in titrations to
a handful
Argentometric Titrations- titrations with silver nitrate
Methods:
1. Volhard Method
2. Fajans Method
3. Mohr Method
Volhard Method
The Volhard method of Ag+ determination is associated with argentometric
titrations even though the titrating agent is actually SCN :
Volhard titration rxn
Ag+
+ SCN AgSCN(s)
analyte
titrant
The indicator in Volhard titrations is Fe3+, which reacts with titrant to form a
red- colored complex:
Volhard indicator rxn
Fe3+
+
indicator
SCNtitrant
Fe(SCN)2+(aq)
red complex
This is a good method for the analysis of Ag + in solution. We can extend the
applicability of this method to anions such as I through the procedure known
as back-titration. A measured excess of Ag+ is added to the dissolved sample:
Ag+
+ I
excess reagent analyte
AgI(s)
dichlorofluorescein
Adsorption indicator, an organic compound that adsorbs onto or desorbs
from the surface of the solid in a precipitation titration. Ideally,the adsorption or
desorption occurs near the equivalence point and results not only in a color
change but also in the transfer of color from the solution to the solid or vice
versa.
The doubly charged dichlorofluoroscein anion is attracted into the
counterion layer immediately following the equivalence point, when the surface
charge of the particles changes from negative to positive. For reasons that are
not fully understood, the closer proximity of the dye to the particles changes the
color of the molecule, providing a visual indication of the titration endpoint. In
the case of dichlorofluorescein, the indicator changes to a pinkish color.
Mohr Method
-Determination of chlorides by titration with silver nitrate
- oldest titration still in use
- researched and published by Karl Friedrich Mohr in 1856
- Chloride is titrated with silver nitrate AgNO3 in the presence of chromate
anions
- end point is signalled by the appearance of the red Ag 2CrO4
Titration reaction:
Ag+ + Cl- AgCl(s)
Ksp = 1 x 10-10
Indicator reaction:
2Ag+ + CrO42- Ag2CrO4(s)
Ksp = 1 x 10-12
Complexometric
titrations
M+L
ML
.
M + Ln-1
MLn
EDTA = H4Y
-The hydrogens in H4Y refer to the 4 ionizable hydrogens
belonging to the 4 carboxylic acid groups
-at sufficiently low pH, the nitrogens can also be protonated and
this diprotonated EDTA can be considered a hexaprotic acid.
However, this occurs at a very low pH and EDTA is almost never
used under such conditions
-It is the unprotonated ligand Y4- that forms complexes with metal
ions, that is, the protons are displaced by the metal ion upon
complexation
-Y4- combines with metal ions in 1:1 chemical equivalence
regardless of the charge of metal ions.
Structure of EDTA-metal
complex
Titrant (Mg-EDTA):
Mg2+ + H2Y2- (excess) MgY2- + 2H+
Titrand (Ca-EBT):
Ca2+ (excess) + H2In- CaIn-
Titration:
Ca2+ + H2Y2- CaY2- + 2H+
Ca2+ + MgY2- CaY2- + Mg2+ (displacement)
CaIn- + H2Y2- CaY2- + H2InEnd point:
H2In- + Mg2+
MgIn- + H2Y2
MgIn- + 2H+
MgY2 + H2In-
(wine red)colorles(blue)
+ 2H+
Eriochrome Black
T
Water hardness
- is the total concentration of alkaline
which are mainly Ca2+ and Mg2+, in water.
earth
(Group
2)
ions,
Good
Beneficial to irrigation
EDTA titration
Initially (before EDTA is added):
M2+ + dye (blue) M2+ - dye (red)
When you begin to add EDTA:
M2+ + EDTA M-EDTA
M2+ + dye (blue) M2+ - dye (red)
At equivalence ([EDTA]=[M]):
M2+ + EDTA M-EDTA
Dye (blue)
This only works if
the EDTA binds the metal better than the indicator!
Titration is carried out at pH 10, in a NH3/NH4+ buffer, which keps the EDTA
(H4Y) mainly in the form HY3-, where it complexes the Group2 ions very well
but does not tend to react as readily with other cations such as Fe 3+ that might
be present as impurities in the water
Titration
HY3- (aq) + Ca2+ (aq) CaY2- (aq) + H+ (aq)
End Point
HY3- (aq) + MgIn- (aq) MgY2- (aq) + HIn2- (aq)
wine red
sky blue
Since the indicator requires a trace of Mg 2+ to operate a little magnesium ion
will be added to each solution. The effect of the added Mg 2+ can be subtracted
by titrating a blank
Redox Titrations
Three types of visual indicators are used to signal the end point in a
redox titration.
Ideal indicator: transition potential should fall within the steep equivalence point
break.
Interference:
4MnO4- + 2H2O 4MnO2 + 3O2 + 4OH(catalyzed by light, heat, acids, bases, MnO2, Mn2+)
Determination of Oxalate
Is important because it is toxic. The
toxicity of oxalic acid is due to kidney
failure caused by precipitation of
solidcalcium oxalate.
Oxalic acids main applications include
cleaning and bleaching especially in
removal of rust
Redox half reactions:
H2C2O4 CO2 + 2H++ 2e-