Volumetric titrimetry

TITRANT By accurately measuring the volume of titrant That is added, the amount of sample can be determined Typically a strong base or acid with known concentration

ANALYTE Can be either a strong or weak acid or base.

Acid-Base Titration
1. Strong acid vs. strong base
13

HCl + NaOH NaCl + H2O There are three events happen during the titration: 1st event: prior to equivalence point
pH equals the amount of sample present after accounting for dilution base (mL) [H3O+] = mmoles acid mmoles base total volume

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pH

Acid-Base Titration
1. Strong acid vs. strong base
13

11

pH

2nd event: equivalence point

[H3O+] = [OH-] pKw = 14 = pH + pOH pH = 7.00 For strong acid/base titration, the pH at the equivalence point is always 7.00 base (mL)

Acid-Base Titration
1. Strong acid vs. strong base
13

3rd event: overtitration

We dont have any acid remaining. All that we are doing is diluting our titrant. [OH-] = mmoles excess total volume pH = 14 - pOH

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pH

base (mL)

Acid-Base Titration
1. Strong acid vs. strong base
13

11

pH

base (mL)

Acid-Base Titration
1. Strong acid vs. strong base

Acid-Base Titration
1. Strong acid vs. strong base 100%
point
13

titration = equivalence

We know that pH = 7.00 Note that for the first 90% of our titration, we only saw a change of 1.28 pH units Now we have a jump of 4.72 pH units.

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pH

base (mL)

Acid-Base Titration
1. Strong acid vs. strong base
13

11

pH

base (mL)

Acid-Base Titration
1. Strong acid vs. strong base

Acid-Base Titration
Okay, it looks easy...what if a strong base is titrated with a strong acid? Well, this is not significantly different with our earlier example. If you plot pOH rather than pH, the results would look identical. Typically we still plot pH vs. ml titrant, so the curves are inverted.

Acid-Base Titration
2. Strong acid or base vs. weak acid or base This type of titration is a bit more complex than the strong acid/base titration. You must consider the fact that weak acids/bases are not completely dissociated in water. Weak acids: HA + H2O Example: CH3COOH Weak bases: BOH Example: NH4OH H3O+ + AH3O+ + CH3COOB+ + OHNH4+ + OH-

Since weak acids and bases are not 100% dissociated in water, they have dissociation constants:

Buffer solution: weak acid and base conjugate CH3COOH + CH3COO - + H2O H3O+ NaOH Na+ + CH3COONa OH- CH3COO - + followed by hydrolisis of Na+ acetate ion + CH3COO H2O CH3COOH OH+

-log [H3O+ ] Henderson-Hasselbalch Equation

Buffer solution: weak base and acid conjugate NH3 + NH4+ + H3O+ HCl H2OCl + H+ NH4+ + ClNH4Cl followed by hydrolisis of ammoniumH2O NH4+ + ion NH3 + H3O+

Henderson-Hasselbalch Equation

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

base (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

acid (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

titrant (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

Remember that Kw = Ka . Kb
titrant (mL)

Kw = 1 x 1014

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

base (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

13

11

pH

titrant (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Kb

Acid-Base Titration
2. Strong acid or base vs. weak acid or base
13

11

pH

X (10/210)

titrant (mL)

Acid-Base Titration
2. Strong acid or base vs. weak acid or base

Redox Titration

Redox Titration

How to balance redox reactions HalfReaction Method 1. Separate the reaction. 2. Balance the atoms. 3. Balance the charge. 4. Add the half-reaction. 5. Check your work. Example: Fe2+ + Cr2O72- Fe3+ + Cr3+

Redox Titration
How to balance redox reactions HalfReaction Method Cr2O72- Fe2+ + Fe3+ + Cr3+ 1. Separate the reactions. Fe2+ Fe3+ Cr2O72- Cr3+ 2. Balance the atoms. Fe2+ Fe3+ Cr2O72- + 14H+ 2Cr3+ + 7H2O 3. Balance the charge. Fe2+ Fe3+ + e} x6 6e- + Cr2O72- + 14H+ 2Cr3+ + 7H2O 1

} x

Redox Titration
A volumetric analysis that relies on a net change in the oxidation number of one or more species. Your titrant is commonly an oxidizing agent although reducing titrants can be used. This unit will cover: Equilibrium and titration calculations Indicators and common titrants Methods of sample preparation

Redox Titration
1.8

1.6

1.4

E (volts)

1.2

overtitrati on prior to equivalent point equivalence point

1.0

0.8

0.6

titrant (mL)

Nernst Equation

Summing the two expressions: At the equivalent point:

an d

known value

known value

Remember: you need to balance the charges in order to get the correct n value

Redox Titration

0.0592 7

Redox Titration

prior to equivalent point

prior to equivalent point

Redox Titration

0% titration, no redox reaction, nothing you can do, so just relax

Redox Titration
prior to equivalent point

Redox Titration
prior to equivalent point

Redox Titration

Redox Titration

0.1 M

Redox Titration

why does it decrease?

Redox Titration

Redox Titration

Redox Titration