CHAPTER 16D

BACK TITRATION
 Back Titration
❑ A known, accurately measured excess of a reagent is
added to the analyte.
❑ A portion of this added reagent reacts with the analyte
and the unreacted portion (or the excess) is determined
from the amount of titrant (back-titrant) consumed.

R&A Addition Rxn: aA + rR ⎯→ pP

Back-titration Rxn: xR + tT ⎯→ nN
Note: The substance that appears on both reactions is the reagent R. The reagent
R is also the substance that is back-titrated.
 Back Titration
Total Amount Amount Amount (mmole) R
(mmole) R (mmole) R unreacted or excess
added = reacted with A + (back-titrated with T)

Molarity Volume (mL) (added as solution)

1 mole of R 1000 mmole

weight of solute (g)  
M.M. of R (g) 1 mole

(added as primary standard)

 Back Titration
Total Amount Amount Amount (mmole) R
(mmole) R (mmole) R unreacted or excess
added = reacted with A + (back-titrated with T)

Molarity  Volume (mL)  SMR

1 mole of A 1000 mmole

weight of solute (g)   SMR 
M.M. of A (g) 1 mole
 Back Titration
Total Amount Amount Amount (mmole) R
(mmole) R (mmole) R unreacted or excess
added = reacted with A + (back-titrated with T)

MTITRANTVTITRANT  SMR
 Standardization and Back Titration
A 0.3207 g sample of primary standard grade benzoic
acid, C6H5COOH, was dissolved in 50.00 mL solution of
Ba(OH)2. The excess base required 4.20 mL of 0.1104 M
HCl for back titration. Calculate the concentration of the
Ba(OH)2 solution.
Titrant

R&A Addition Rxn: Ba(OH)2 + 2C6H5COOH ⎯→ Ba(C6H5COO)2 + 2H2O

Back-titration Rxn: Ba(OH)2 + 2HCl ⎯→ BaCl2 + H2O

 Back Titration
R&A Addition Rxn: Ba(OH)2 + 2C6H5COOH ⎯→ Ba(C6H5COO)2 + 2H2O

Back-titration Rxn: Ba(OH)2 + 2HCl ⎯→ BaCl2 + H2O

Total Amount Amount Amount (mmole) R

(mmole) R = (mmole) R
reacted with A
+ unreacted or excess
added (back-titrated with T)
Ba(OH)2 (M x V) BA (m x MM) HCl (M x V)
 Back Titration
R&A Addition Rxn: Ba(OH)2 + 2C6H5COOH ⎯→ Ba(C6H5COO)2 + 2H2O

Back-titration Rxn: Ba(OH)2 + 2HCl ⎯→ BaCl2 + H2O

BA (m x MM)
HCl (V x M)
0.3207 g BA 1 mol BA 1 mol Ba(OH)2
122.12 g BA 2 mol BA +
0.1104 mol HCl 1 mol Ba(OH)2
0.00420 L HCl
L HCl 2 mol HCl

0.05000 L Ba(OH)2
= 0.0308979 = 0.0309 M
 Typical Application of Back Titration –
Kjeldahl Method
digestion distillation
Bound N NH4+ NH4+ NH3
 Typical Application of Back Titration –
Kjeldahl Method
If the acid trap is HCl or
H2SO4 then the Kjeldahl
digestion distillation method is classified as
back titration method

NH4OH + H3O+

NH4Cl + H2O
 Kjeldahl Method
A 1.00 mL aliquot of fish oil was analyzed for N using the
Kjeldahl method. After digestion, the distilled ammonia
was collected in 100.00 mL of 0.05030 M HCl. The excess
HCl required 28.30 mL of 0.1240 M NaOH for titration.
Calculate the amount of N in the sample as mg N/mL.
Titrant

R&A Addition Rxn: HCl + NH3 ⎯→ NH4Cl

Back-titration Rxn: HCl + NaOH ⎯→ NaCl + H2O

 Kjeldahl Method

Total Amount Amount Amount (mmole) R

(mmole) R = (mmole) R
reacted with A
+ unreacted or excess
added (back-titrated with T)

Amount Total Amount Amount (mmole) R

(mmole) R = (mmole) R - unreacted or excess
reacted with A added (back-titrated with T)
NH3 (n) HCl (V x M) NaOH (V x M)
 Back Titration
R&A Addition Rxn: HCl + NH3 ⎯→ NH4Cl

Back-titration Rxn: HCl + NaOH ⎯→ NaCl + H2O

HCl (V x M) NaOH (V x M) NH3 (n)
100.00 mL 0.05030 mmol HCl 1 mmol NH3 1 mmol N
HCl 1 mL HCl 1 mmol HCl 1 mmol NH3

28.30 mL 0.1240 mmol NaOH 1 mmol HCl 1 mmol NH3 14 mg N

- NaOH 1 mL NaOH 1 mmol NaOH 1 mmol HCl 1 mmol N

1 mL fish oil
= 21.291200 = 21.29 mg N / mL fish oil
 Typical Application of Back Titration –
Saponification
❑ Saponification is used in determining organic and
biochemical substances
❑ Saponification is a process by which an ester is
hydrolyzed in alkaline solution to give an alcohol
and a conjugate base
• The sample (ESTER) is heated in the presence of an accurately
measured amount of a standard base.
• The hydrolysis or SAPONIFICATION consumes one mole of
base per mole of ester
• After the saponification is judged to be complete the excess base
is titrated with a standard acid solution
 Saponification
A 0.8160 g sample of dimethylphthalate, C6H4(COOCH3)2
(Molar Mass = 194.19), and unreactive species was refluxed
with 50.00 mL of 0.1031 M NaOH to hydrolyze the ester groups

C6H4(COOCH3)2 + 2OH− ⎯→ C6H4(COO)2 2− + 2CH3OH

After the reaction was complete, the excess NaOH was back-
titrated with 24.27 mL of 0.1644 M HCl.

Calculate the percentage of dimethylphthalate in the sample.

 Typical Application of Back Titration –
Sulfur Analysis
❑ The sulfur present in organic and biological
materials is determined by burning the sample in a
stream of oxygen gas.
❑ The products are sulfur dioxide (SO2) and sulfur
trioxide (SO3).
❑ The gaseous products are collected by distillation into
a dilute solution of H2O2 forming sulfuric acid, H2SO4.
TITRATED WITH A
SO2 + H2O2 ⎯→ H2SO4
STANDARD BASE

H2SO4 + 2NaOH ⎯→ Na2SO4 + 2H2O