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Application Note
Determination of mixed acids (nitric acid, phosphoric acid,
acetic acid) in etchant for aluminum
Industry : Metals
Instrument : Automatic potentiometric titrator
Measurement method : Potentiometric titration / Neutralization titration
Standards : -
1. Scope
Nitric acid, phosphoric acid and acetic acid are contained as an acidic component in the etchant under
manufacturing process of aluminum. Each concentration in the acidic component affects the performance
and property of the etchant. Therefore, controlling the concentration of each component is important.
In this application note, determination of nitric acid, phosphoric acid and acetic acid concentration in a
non-aqueous solvent by neutralization titration are described. Strength of the each acid in water can not
be detected separately, however, in organic solution, it can be detected separately and this phenomenon is
taken in this application. In this titration method, three end-points are detected. Each end point
corresponds to the following chemical reaction.
HNO3＋KOH→KNO3+H2O Titer volume consumed by the 1st end point
H3PO4+KOH→KH2PO4+H2O Titer volume consumed by 1st～2nd end point
CH3COOH+KOH→CH3COOK+H2O Titer volume consumed by 2nd ～3rd end point
2. Precautions
1) The standardization of the titrant is in accordance with JIS K 8001 or ISO 6531-1.
2) Store the titrant in a container made of resin. Please attach the Zeolite cylinder to suppress
the intrusion of carbon dioxide.
3. Post-measurement procedure
After measurement, wash the electrode with pure water. After that, please immerse the electrode in
pure water and keep it.
4. Apparatus
Main unit : Automatic potentiometric titration system (preamplifier:STD)
Electrode : Combined Glass Electrode
(Internal liquid of reference electrode: 1 mol / L lithium chloride / ethanol solvent)
5. Reagents
Titration solution: 0.1 mol / L potassium hydroxide (ethanol solution)
Titration solvent: Propylene glycol and ethanol mixed in the same volume
6. Procedure
- Measurement -
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1) Weigh approximately 0.5 g of sample into a 200 mL beaker.
2) Add about 100 mL titration solvent and dissolve the sample.
3) Titrate with 0.1 mol / L potassium hydroxide (ethanol solution).
7. Calculation
HNO3(wt% ) = ( EP1 － BL1 ) × TF1 × C1 × K1 / S
H3PO4(wt% ) = ( EP2 － EP1 － BL1 ) × TF1 × C2 × K1 / S
CH3COOH(wt% ) = ( EP3 － EP2 － BL1 ) × TF1 × C3 × K1 / S
EP1 ：Titer volume consumed by the 1st end point( mL )
EP2 ：Titer volume consumed by the 2nd end point( mL )
EP3 ：Titer volume consumed by the 3rd end point( mL )
BL1 ：Blank value( 0.000mL )
TF1 ：Factor value of titrant（1.0340）
C1 ：Concentration conversion factor 1(6.300 mg/mL )
C2 ：Concentration conversion factor 2( 9.800 mg/mL )
C3 ：Concentration conversion factor 3( 6.005 mg/mL )
K1 ：Unit conversion factor(0. 1 )
S ：Sample size(ｇ)
8. Example
-Titration parameter-
＜Titr.Mode＞ :Auto Intermit ＜Ctrl.Para＞
Number of EP ：3
＜Titr.Form＞ :EP Stop End Sense ：Set
dE ：20dE
＜Titr.Para＞ :1 dmL ：30dE/dmL
Burette No. : 80(mL) Gain ：1
Max. Volume : Ch1, pH Stirrer Speed ：4
Channel/Unit(Ctrl.) : Off Data sampling ：standard
Channel/Unit(Ref.) : standard Ctrl. Speed ：standard
pH Polarity : Negative Other Control ：standard
Titr.Type Check : Auto
Direction : 3 (s)
Wait Time ：None
(The measurement parameter and the titration curve are an example.)
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-Titration curve and results-
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Five types of samples (●, ■, ▲, ○, △) were prepared and titrated. The measurement results are
shown in Table 1.
Table1 Measurement result of each sample
nitric acid phosphoric acid Acetic acid
Sample Absolute Absolute Absolute
symbol concentration Average concentration Average concentration Average
error error error
(%) value (%) (%) value (%) (%) value (%)
(%) (%) (%)
▲ 6.65 6.69 -0.04 29.58 29.79 -0.21 30.28 30.91 -0.63
■ 8.31 8.37 -0.06 15.10 15.47 -0.36 61.60 62.87 -1.28
● 11.67 11.78 -0.11 10.23 10.63 -0.40 4.14 4.20 -0.06
○ 0.99 0.96 0.03 60.01 60.42 -0.42 14.31 14.57 -0.26
△ 3.02 3.00 0.02 60.24 60.90 -0.66 1.04 1.08 -0.04
Correlation
1.0000 - 1.0000 - 1.0000 -
coefficient
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Table 2 shows detailed measurement results of each sample.
Table 2 Details of measurement results
of each sample nitric phosphoric Acetic
Sample Sample Titrant EP1 EP2 EP3
acid acid acid
symbol (g) Factor Titer (mL) Titer (mL) Titer (mL)
(wt%) (wt%) (wt%)
1 0.4527 1.0340 4.6493 6.69 17.9383 29.75 40.4771 30.91
2 0.4210 1.0340 4.3138 6.67 16.6736 29.75 37.7722 31.12
3 0.4206 1.0340 4.3215 6.69 16.7168 29.86 37.5139 30.70
▲ Mean(wt%) - - - 6.69 - 29.79 - 30.91
S.D.(wt%) - - - 0.01 - 0.07 - 0.21
R.S.D.(%) - - - 0.15 - 0.22 - 0.67
MAX-MIN(wt%) - - - 0.02 - 0.12 - 0.42
1 0.4370 1.0340 5.6033 8.35 12.2516 15.42 56.1940 62.44
2 0.4174 1.0340 5.3682 8.38 11.7725 15.55 54.1236 63.00
3 0.4153 1.0340 5.3460 8.39 11.6714 15.43 53.9290 63.18
■ Mean(wt%) - - - 8.37 - 15.47 - 62.87
S.D.(wt%) - - - 0.02 - 0.07 - 0.39
R.S.D.(%) - - - 0.21 - 0.46 - 0.62
MAX-MIN(wt%) - - - 0.03 - 0.13 - 0.74
1 0.4456 1.0340 8.0615 11.79 12.7429 10.65 15.7251 4.16
2 0.4671 1.0340 8.4363 11.77 13.3425 10.64 16.5074 4.21
3 0.4863 1.0340 8.7997 11.79 13.8880 10.60 17.2069 4.24
● Mean(wt%) - - - 11.78 - 10.63 - 4.20
S.D.(wt%) - - - 0.01 - 0.02 - 0.04
R.S.D.(%) - - - 0.10 - 0.23 - 0.99
MAX-MIN(wt%) - - - 0.02 - 0.04 - 0.08
1 0.5196 0.9935 0.7974 0.96 33.1008 60.53 45.7143 14.48
2 0.5237 0.9935 0.8049 0.96 33.3279 60.47 46.1954 14.66
3 0.5197 0.9935 0.7940 0.96 32.9639 60.27 45.6523 14.57
○ Mean(wt%) - - - 0.96 - 60.42 - 14.57
S.D.(wt%) - - - 0.00 - 0.14 - 0.09
R.S.D.(%) - - - 0.31 - 0.23 - 0.60
MAX-MIN(wt%) - - - 0.01 - 0.26 - 0.18
1 0.5371 0.9935 2.5577 2.98 36.1562 60.91 37.1457 1.10
2 0.5458 0.9935 2.6202 3.00 36.7371 60.86 37.7501 1.11
3 0.5286 0.9935 2.5370 3.00 35.6176 60.93 36.5301 1.03
△ Mean(wt%) - - - 3.00 - 60.90 - 1.08
S.D.(wt%) - - - 0.01 - 0.04 - 0.04
R.S.D.(%) - - - 0.46 - 0.06 - 3.94
MAX-MIN(wt%) - - - 0.02 - 0.07 - 0.08
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9. Summary
Measurement result of nitric acid concentration was obtained with good accuracy.
However, measurement result of phosphoric acid and acetic acid tends to be larger
deviation when these concentrations are higher. Therefore, the accuracy of these acids
became worse than nitric acids. However, the difference between the maximum and
minimum is only at most about 0.7 wt%, therefore, it is considered that these results are
also obtained with sufficient accuracy.
This method is effective and easy method to determine the concentration of each acids
without any requirement of complicated preparation process. However, the detection
limit and accuracy depend on the concentration. In case that sample testing is necessary
to verify if this method is effective, please contact us.
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