Titration Application Note

Determination of Peracetic Acid by

Note

Potentiometric Titration
Titration Application

Introduction Sample Preparation and Procedures

Peracetic acid (also peroxyacetic acid, PAA, 1. Approx. 250 mg of the sample mixture are
CH3COOOH) can be obtained by mixing hydrogen accurately weighed into a titration beaker.
peroxide with acetic acid (AcOH). Because of its 2. The sample is diluted with approx. 40 mL deion.
strong oxidizing character, PAA is often used as water
bleach or disinfectant. The main field of application 3. The diluted sample is titrated with 0.5 M NaOH
is the sterilization of plastic bottles in the bottled solution
beverage production. 4. The titration head is rinsed with deion. water
Upon mixing hydrogen peroxide and acetic acid, directly in the sample beaker after every sample.
the following equilibrium is slowly settled:
Chemistry
𝐶𝐻3 𝐶𝑂𝑂𝐻 + 𝐻2 𝑂2 →
← 𝐶𝐻3 𝐶𝑂𝑂𝑂𝐻 + 𝐻2 𝑂 Acetic acid and peracetic acid content as mmol/g
sample and %.
The formation of this equilibrium is very slow but
can be accelerated by the presence of strong acids. CH3COOH, M = 60.05 g/mol, z = 1
Solutions with PAA contents between 2.5 and 40 CH3COOOH, M = 76.05 g/mol, z= 1
% are commercially available. A dilution of the
mixture with water leads to a new equilibrium with Neutralization reactions:
a lower PAA content. CH3COOH + NaOH → CH3COO- + Na+ + H2O
The determination of PAA is commonly performed CH3COOOH + NaOH → CH3COOO- + Na+ + H2O
by redox titrations. PAA oxidizes iodide to iodine,
which is then titrated with thiosulfate. The hydrogen Solutions
peroxide, which is always present in the solution  Titrant: Sodium hydroxide, NaOH,
needs to be titrated first, e.g. with potassium c(NaOH) = 0.5 mol/L
permanganate, because it interferes with the  Chemicals: Deionized water
iodometric titration. Apart from the high complexity,  Standard: Potassium hydrogen phthalate,
this method has the drawback that it relies on the KHP, 80 mg
use of sulfuric acid, which catalyzes a shift of the
equilibrium to lower PAA contents during the Instruments and Accessories
 Titration Excellence T5 (30252672), T7
sample preparation.
(30252675) or T9 (30252676)
Alternatively, the mixture can be titrated with a
 XP205 Analytical balance (11106027)
strong base such as NaOH. The large difference
 InMotion Flex Base (30094121)
between the pKa values of AcOH (4.75) and PAA
 InMotion Flex Rack Kit 100 mL (30094126)
(8.2) enables the determination of both species
 SD660 diaphragm pump (30094165) for
using a single titration. If performed quickly, the PowerShower rinsing (included in InMotion
dilution of the sample barely affects the equilibrium Pro Base delivery
between AcOH and PAA.  DGi111-SC Combined pH glass electrode
This application describes the determination of (51109500)
AcOH and PAA in a single titration using aqueous  Compact Stirrer (51109150)
NaOH as titrant.  LabX software
 Titration beakers PP 100 mL (101974)

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M795 v1.0
 Results evaporation. The titration should be performed
Titration Application Note

The AcOH and PAA contents were determined as rapidly as well to prevent the equilibrium shift upon
mmol/ g sample and % for a series of 6 samples. dilution of the sample solution.

AcOH content: The identity of the titrated acids can be verified by

R2: Content R3: Content Sample their half-neutralization points (EHNV), which are
AcOH AcOH Weight reported by the titrator and correspond to the pKa
[%] [mmol/g] [g] values of the titrated acids. Accordingly, it is
1 38.176 6.357 0.2953 preferential to display the titration curve in pH
2 37.990 6.326 0.2438 values vs. titrant volume using a freshly calibrated
3 38.066 6.339 0.2700 pH electrode.
4 38.280 6.375 0.2552
5 38.058 6.338 0.2492 This application note has been developed for the
6 37.985 6.325 0.2667 mentioned sample. It may be necessary to optimize
Mean 38.092 6.343 the method for other samples.
s 0.115 0.019
srel 0.302 % 0.305 %
Waste disposal and safety measures
PAA content: AcOH and PAA are both flammable and corrosive.
R2: Content R3: Content Sample Hydrogen peroxide and PAA are strong oxidants. In
PAA PAA Weight higher concentrations, PAA can undergo explosive
[%] [mmol/g] [g] decomposition when heated.
1 12.937 1.701 0.2953
2 13.008 1.710 0.2438 Wear personal protection at all times while in the
3 13.088 1.721 0.2700 laboratory, i.e. safety glasses, lab coats and
4 13.137 1.727 0.2552 gloves. Read and understand the appropriate
5 13.055 1.717 0.2492 MSDS's when using chemicals prior to use.
6 12.993 1.708 0.2667
Mean 13.036 1.714 Dispose the sample solutions as aqueous acid-
s 0.072 0.009 base solutions.
srel 0.550 % 0.552 %
References
[1] Anal. Methods, 2014, 6, 2406
Remarks
This method has been developed using an Further information
Excellence Titrator with the InMotion autosampler. http://www.mt.com/global/en/home/products/Labo
However, it can easily be adapted and used for ratory_Analytics_Browse/Product_Family_Browse_
Compact Titrators G10S (30267117) and G20S titrators_main/Titration_Excellence.html
(30252669) with the Rondolino autosampler
(51108500) or with the manual titration stand.

This application was described before in more

detail.1 It has been shown that the equilibrium of
AcOH and PAA was not affected by the sample size
or dilution volume, respectively.

After weighing in the sample, it should be diluted

with water quickly to avoid a loss of sample by

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 Measured values
Titration Application Note

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Titration Application Note
Time Volume E ∆V dE dE/dV Temperature
[s] [mL] [pH] [mL] [pH] [pH/mL] [°C]
0 0 3.098 - - - 25
3 0.01 3.118 0.01 0.020 - 25
6 0.02 3.137 0.01 0.019 - 25
9 0.0450 3.192 0.025 0.055 - 25
12 0.0995 3.315 0.0545 0.123 - 25
15 0.1590 3.437 0.0595 0.122 1.86 25
19 0.2340 3.572 0.0750 0.135 1.60 25
… … … … … …
81 3.5305 6.060 0.0555 0.140 3.20 25
84 3.5735 6.201 0.0430 0.141 3.84 25
87 3.6060 6.335 0.0325 0.134 4.41 25
90 3.6330 6.469 0.0270 0.134 4.97 25
94 3.6560 6.599 0.0230 0.130 5.54 25
97 3.6780 6.733 0.0220 0.134 5.86 25
3.680270 6.747 5.86 EQP1
100 3.6995 6.863 0.0215 0.130 5.68 25
103 3.7225 6.997 0.0230 0.134 5.21 25
106 3.7475 7.123 0.0250 0.126 4.68 25
110 3.7795 7.266 0.0320 0.143 4.09 25
113 3.8145 7.395 0.0350 0.129 3.55 25
116 3.8605 7.538 0.0460 0.143 2.99 25
… … … … … …
149 4.5325 8.983 0.0470 0.144 3.66 25
152 4.5710 9.127 0.0385 0.144 4.39 25
155 4.6015 9.270 0.0305 0.143 5.09 25
159 4.6255 9.406 0.0240 0.136 5.72 25
162 4.6455 9.535 0.0200 0.129 6.34 25
166 4.6650 9.673 0.0195 0.138 6.76 25
4.6650 9.673 6.76 EQP2
169 4.6830 9.800 0.0180 0.127 6.55 25
172 4.7030 9.934 0.0200 0.134 5.90 25
176 4.7250 10.063 0.0220 0.129 5.23 25
179 4.7520 10.198 0.0270 0.135 4.57 25
183 4.7850 10.329 0.0330 0.131 3.87 25
186 4.8290 10.466 0.0440 0.137 3.14 25
… … … … … …
265 9.1095 12.442 0.2000 0.030 0.14 25
268 9.3095 12.469 0.2000 0.027 - 25
271 9.5095 12.495 0.2000 0.026 - 25
274 9.7095 12.520 0.2000 0.025 - 25
277 9.9095 12.543 0.2000 0.023 - 25
280 10.0000 12.559 0.0905 0.016 - 25

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 Termination
Method
Titration Application Note
At Vmax [mL] 10
At potential No
001 Title At slope No
Type General titration After number of recognized EQPs No
Compatible with T5/T7/T9 Combined termination criteria No
Title PAA Termination
Accompanying stating No
Termination
002 Sample
Condition No
Sample type Sample
Number of IDs 1
006 Rinse (Rinse1)
ID 1 PAA
Entry type Weight Auxiliary reagent Water
Lower limit [g] 0.0 Rinse cycles 1
Upper limit [g] 5.0 Vol. per cycle [mL] 15
Density [g/mL] 1.0 Position Current position
Correction factor 1.0 Drain No
Temperature [°C] 25.0 Condition No
Entry Arbitrary
InMotion reader None 007 Consumption AcOH (R1)
Number of sample factors 0 Result Consumption AcOH
Result unit mL
003 Titration stand (Titrationstand1) Formula R1 = VEQ
Type InMotion T/Tower A Constant C = 1
Titration stand InMotion T/1A M M[None]
Head position Sample z z[None]
Lid handling No Decimal places 3
Result limits No
Record statistics No
004 Stir (Stir1)
Extra statistical functions No
Speed [%] 30 Send to buffer None
Duration [s] 30 Condition No
Condition No

008 Content AcOH (R2)

005 Titration (EQP) [1] (TitrationEQP1)
Result Content AcOH
Titrant Result unit %
Titrant NaOH Formula R2 = Q*C/m
Concentration [mol/L] 0.5 Constant C= M/(10*z)
Sensor M M[Acetic acid]
Type pH z z[Acetic acid]
Sensor DGi111-SC Decimal places 3
Unit pH Result limits No
Temperature acquisition Record statistics No
Temperature measurement No Extra statistical functions No
Stir Send to buffer None
Speed [%] 30 Condition No
Predispense
Mode None
009 Content AcOH (R3)
Wait time [s] 0
Control Result Content AcOH
Control User Result unit mmol/g
Titrant addition Dynamic Formula R3 = Q*C/m
dE (set value) [mV] 8.0 Constant C= 1/z
dV (min) [mL] 0.01 M M[Acetic acid]
dV (max) [mL] 0.2 z z[Acetic acid]
Mode Equilibrium controlled Decimal places 3
dE [mV] 0.5 Result limits No
dt [s] 1 Record statistics No
t (min) [s] 3 Extra statistical functions No
t (max) [s] 30 Send to buffer None
Evaluation and recognition Condition No
Procedure Standard
Threshold [mV/mL] 3
Tendency Positive
Ranges 0
Add. EQP criteria Steepest jump
Steepest jumps 2

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 010 Consumption PAA (R4)
Titration Application Note

Result Consumption PAA

Result unit mL
Formula R4 = VEQ2
Constant C = 1
M M[None]
z z[None]
Decimal places 3
Result limits No
Record statistics No
Extra statistical functions No
Send to buffer None
Condition No

011 Content PAA (R5)

Result Content PAA
Result unit %
Formula R5 = Q2*C/m
Constant C= M/(10*z)
M M[Peracetic acid]
z z[Peracetic acid]
Decimal places 3
Result limits No
Record statistics No
Extra statistical functions No
Send to buffer None
Condition No

012 Content PAA (R6)

Result Content PAA
Result unit mmol/g
Formula R6 = Q2*C/m
Constant C= 1/z
M M[Peracetic acid]
z z[Peracetic acid]
Decimal places 3
Result limits No
Record statistics No
Extra statistical functions No
Send to buffer None
Condition No

013 Record (Record1)

Report template Titration report
Print No
Condition No

014 End of sample

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