Acid Mixtures Guide

Competence Guide
Simultaneous
Determination
of Acid Contents
in Mixtures
Titration Excellence
T5 / T7 / T 9
Titration of Acid Mixtures

Electroplating, Electronics and Metal Industry
Editorial
Competence Guide
Technology and its products have become indispensable parts of daily life: among many others,
transportation vehicles such as cars, trains, trucks and planes are irreplaceable, home appliances facilitate
household work, and computers are quickly leading the society into the digitalization age. In particular,
the world of communication has experienced the deepest transformation: thanks to Internet and mobile
phones the way of communicating has become faster and independent on time and location.
If software is the soul of electronics devices, hardware represents their body. They can smoothly function
if their electronic and metal components such as semiconductors, printed circuits and housings meet the
required quality standards. The quality during production has to be periodically monitored by analytical
techniques. Titration, a well-known method for quantitative analysis, plays a key role in the quality control
in production plants of the electroplating, semiconductors and metal processing industries. Beside the
control of different metal ion contents, the degree of acidity of electroplating baths used in the production
process has to be constantly monitored to ensure high quality products.
Generally, acid mixtures consisting of 2-3 acids such as sulfuric, nitric and hydrochloric acids are
commonly used in production processes. Hence, the exact knowledge of the content of each single acid
component is crucial for workflow optimization. However, the titration of acid mixture generally does not
lead to more than one equivalence point i.e. it is not possible to always determine the content of all acids
with a single titration in aqueous solution. In fact, the appearance of a potential jump at the equivalence
point in the titration curve during titration strongly depends on the acid strength in the specific solvent.
This can be overcome by optimizing the choice of the solvent and of the titrant. This Guide covers selected
applications and background information for the simultaneous titration of the acid components in a mixture
with Titration Excellence T5, T7 and T9. The Guide consist of three parts:
 Selected titration applications:
The results for typical acid mixtures such as HCl/HNO3 and CH3COOH/H3PO4/HNO3 are
presented. The applications have been developed by the Market Support Group Analytical
Chemistry, and they are available from the Expertise Library on www.mt.com .
 Question on acid/base titrations:
Relevant background information is presented by means of FAQs - frequently asked questions.
 Non-aqueous acid/base titrations:
Fundamental basics on acids and bases in aqueous and non-aqueous solvents are described in
details. This part is completed with recommendations on choice of suitable solvents and titrants
for differentiation of each single acid (base) component of a mixture during titration.
We are convinced that this Guide will support you in your work on content determination in acid mixtures.
Daniel Buchmann Dr. Cosimo A. De Caro

Head Market Support Group Senior Applications Specialist
SBU Analytical Chemistry Market Support Group Analytical Chemistry
METTLER TOLEDO Page 1 of 34

Simultaneous Titration of Acid Mixtures
Contents
Competence Guide
OVERVIEW 3
Motivation ............................................................................................................................................. 3
Titration: What is it? ................................................................................................................................ 3
Titration of acid mixtures ......................................................................................................................... 3
Acid dissociation constant – pKa .............................................................................................................. 4
Strategies for the differentiation of acids in mixtures .................................................................................... 5
Checklist for titrations of acid mixtures ...................................................................................................... 6
SELECTED TITRATION APPLICATIONS 7

Phosphoric acid – H3PO4 ........................................................................................................................ 7
Acetic, phosphoric and nitric acid - CH3COOH : H3PO4 : HNO3 ..................................................................... 9
Acetic, phosphoric, nitric acid: large excess of phosphoric acid - CH3COOH : H3PO4 : HNO3 ......................... 10
Acetic, phosphoric, nitric acid: low concentrations - CH3COOH : H3PO4 : HNO3 ........................................... 11
Sulfuric and phosphoric acids in a polishing bath – H2SO4 : H3PO4 ........................................................... 13
Hydrochloric acid, acetic acid, and ammonium chloride – HCl : CH3COOH : NH4Cl ..................................... 14
Nitric, hydrofluoric and acetic acids in an etching bath - HNO3 : HF : CH3COOH .......................................... 15
Nitric, hydrofluoric and acetic acids in an etching bath - HNO3 : HF : CH3COOH .......................................... 16
Nitric, hydrofluoric and hexafluorotitanic acids - HNO3 : HF : H2TiF6 ........................................................... 17
QUESTIONS ON ACID/BASE TITRATIONS 18

There are strong and weak acids – Why? ................................................................................................ 18
What is happening if an acid is dissolved in water? ................................................................................. 19
What is happening if a base is dissolved in water? .................................................................................. 20
What about other solvents such as e.g. ethanol or methanol? ................................................................... 21
Why do we titrate acid or bases in non-aqueous solvents? ....................................................................... 22
What about solvents that do not dissociate? ............................................................................................ 23
NON-AQUEOUS ACID/BASE TITRATIONS OF MIXTURES 24

Key points and motivation ..................................................................................................................... 24
Titration of acids and acid mixtures in non-aqueous solutions .................................................................. 25
Titration of bases in non-aqueous solutions ............................................................................................ 31
LITERATURE 34

Overview
Competence Guide
Motivation
Acid mixtures are used e.g. in electroplating baths for the surface treatment of metal parts to achieve corrosion
protection and resistance to abrasion. Among other components, the mixtures mainly consist of strong acids such
as hydrochloric HCl, sulfuric H2SO4, hydrofluoric HF and phosphoric acid H3PO4, as well as weak acids such as
acetic acid (CH3COOH). The acid content affects the efficiency and efficacy of the electroplating processes.
Therefore, the monitoring of the acid content is a relevant analysis to ensure product quality.
Titration: What is it?

Titration is a straightforward, easy and affordable technique for the acid content determination in various solutions.
Briefly, the acid content is determined by addition of a strong alkaline solution i.e. sodium or potassium hydroxide
(NaOH or KOH, respectively) to the sample. During titrant addition, the potential difference is monitored with a
potentiometric sensor (a pH electrode), such that the process can be visualized in terms of a (so-called) titration
curve.
The alkaline titrant solution is added until a clear potential change –a potential jump- is observed. In the case of
a single acid present in the sample solution, the titration curve is shows a clear S-shaped profile. The equivalence
point of the titration is located at the inflection point of the curve.
Titration of acid mixtures

In the case where an acid mixture with several different acids is titrated, one would expect a titration curve with
so many potential jumps as the number of acids present in the sample solution. This is the case for the acid
mixture consisting of hydrochloric acid, acetic acid, and ammonium chloride i.e. HCl : CH3COOH : NH4Cl, as
given below:
Fig. 1: Simulated titration curve of 3 mL each of 0.1 M HCl (strong acid), 0.1 M CH3COOH (weak acid strength),
and 0.1 M NH4Cl (very weak acid) in water with 0.1 M NaOH (CurTitPot, http://www.iq.usp.br/gutz/Curtipot_.html).
Here, all acids have the same concentration i.e. 0.1 M, and the same sample size. The mixture, diluted with 50
mL deionized water, is titrated with a strong base such as sodium hydroxide having the same concentration i.e.
0.1 M NaOH. The titration curve shows three potential jumps at 3, 6 and 9 mL titrant consumption. In particular,
each potential jump indicates the equivalence point (EQP) of the corresponding neutralization reaction. The
determined EQP allows for the calculation of the content of each acid.

However, there is still one question that needs to be answered:
Competence Guide
How do we know which potential jump corresponds to which acid?
The sequence of the three potential jumps in the curve is given by the strength of the acids. In fact, the strongest
acid is first neutralized. Subsequently, the neutralization of the weaker acids just occurs once the stronger acid is
neutralized. Overall, acids in a mixture are neutralized successively in the order of their acid strength. In the
HCl:CH3COOH:NH4Cl mixture, the first potential jump corresponds to the strongest acid, HCl, then acetic acid is
neutralized leading to the second jump, and the third one corresponds to the weakest acid NH 4Cl:
HCl CH3COOH NH4Cl

Acid strength
strength
Fig. 2: HCl is the strongest acids compared to acetic acid and ammonium chloride.
Acid dissociation constant – pKa

The strength of an acid is quantified by the acid dissociation constant Ka. Its strength is indicated by the pKa
value, which is the negative logarithm of the dissociation constant Ka of an acid HA:
[𝐻3 𝑂 + ]∙[𝐴− ]
HA + H2O ⇌ H3O+ + A- 𝐾𝑎 = pKa = -log(Ka)
[𝐻𝐴]∙[𝐻2 𝑂]
The pKa values in aqueous solutions of selected acids are given in the following table:
pKa (25° C)
Acid - D.W. Oxtoby et al., "Principle of Modern Chemistry", 3rd ed., Saunders Publ., 1996
Acid strength
- * Wikipedia
HCl -7
H2SO4 -3 pKa1
1.92 pKa2
HNO3 -1.3
H2C2O4 (Oxalic acid) 1.25 * pKa1

4.14 * pKa2
H3PO4 2.12 pKa1

7.21 pKa2
12.67 pKa3
HF 3.18
CH3COOH (Acetic acid) 4.75
CH3COOOH (Peracetic acid) 8.2 *
NH4Cl (Ammonium chloride) 9.24 *
Tab. 1: Acid strength of selected acids:

The lower the pKa value, the stronger the acid, as indicated by the arrow above procedure.

Strategies for the differentiation of acids in mixtures
Competence Guide
The acid mixture 0.1 M HCl:CH3COOH:NH4Cl = 1:1:1 v/v in an aqueous solution represents an ideal mixture for
the determination of the content of each acid by titration. In fact,
• the differences ∆pKa in acid strengths is big,
∆pKa (HCl - CH3COOH) > 11 and ∆pKa (CH3COOH - NH4Cl) > 4 ,
• all three acids have the same concentration, i.e. 0.1 M,
• the mixture consists of the same amounts for each acid, i.e. 3 mL of each acid.
Real samples from electroplating baths seldom have this ideal composition. Usually, the mixtures consist of acids
with similar strengths, different amounts and different concentrations. As a result, the titration curves of the acids
in the mixture are overlapping since some dissociation steps collapse together in a single one. Hence, the resulting
titration curve of an acid mixture does not show the potential jump of each acid.
For this reason, the potential jumps of all acid components in an aqueous mixture are only visible and can be
evaluated by the titrator if
• the pKa values are different by several units i.e. at least 4-5
• the acid concentrations and amounts are more or less the same
Thus, the pKa value is the relevant point to be first checked whenever the titration of acid mixtures in aqueous
solutions is performed.
For the HCl:CH3COOH:NH4Cl mixture, the three potential jumps due to the acids are visible in the titration curve –
as shown in figure 1. In general, this is not the case since the pKa values of the acids in the mixture to be analyzed
are generally too close to each other.
However, it is still possible - to a certain degree - to differentiate the different potential jumps in a titration curve
− by replacing water with a suitable organic solvent
e.g. acetone, 2-propanol, ethanol, methanol and mixtures thereof
and/or
− by adding an inert salt to the aqueous solution to modify its ionic strength.
e.g. potassium chloride KCl and sodium chloride NaCl
This leads for a shift of the pKa values, and therefore the difference between them is increased. For instance, you
can dissolve the sample in e.g. acetone, and titrate with tetraethylammonium or tetramethylammonium hydroxide
in 2-propanol.
In addition, the use of suitable evaluation parameters in the calculation method functions further support the
determination of the equivalence point (EQP) for each single expected potential jump.

In this guide, selected examples of acid mixtures and polyprotic acids titrations are presented to show how to
Competence Guide
cope with titration of these samples. Representative applications thereof are summarized in table 2:
Acid mixtures / Polyprotic acids Titration Solution
Polyprotic acids Titration to all EQPs - Identify the pKa value of each dissociation step
e.g.: - Verify if the values are different by more than
H2SO4 approx. 4-5 pKa units to be visible
H3PO4 - make sure the pKa values are smaller than the
H2C2O4 autodissociation constant of water pKw = 14
- If YES: Try a titration in aqueous solutions
H3PO4 Titration to 3 EQPs - Sample dissolved in saturated NaCl solution

- Two titration (EQP) functions with two different
threshold values
HNO3 : HF : CH3COOH Differentiation - Sample dissolved in acetone:2-propanol 1:1

of 3 EQPs v/v
CH3COOH : H3PO4 : HNO3 Content determination - The differences between the dissociation steps
by evaluation are large enough to get a potential jump.
of 3 EQPs - Identify the pKa value of each dissociation step
in aqueous solution
- Verify if the pKa difference is more than 4-5
- Verify if pKa values are below/very close to the
autodissociation constant of water pKw = 14
CH3COOH : H3PO4 : HNO3 Evaluation - Identify the pKa value of each dissociation step
Large excess of H3PO4 of 3 EQPs - The first derivative curve shows small and
at almost identical peaks for the first two EQPs
specific potential
- These peaks cannot be evaluated using
values
specific threshold values since very small and
close to each other
CH3COOH : H3PO4 : HNO3 Evaluation - Identify the pKa value of each dissociation step
Concentrations below 0.3% of 3 EQPs - The first derivative curve shows two small
with potential ranges peak values for the first two EQPs
- These are evaluated with a potential range
Tab. 2: Simultaneous titrations of acid mixtures and of polyprotic acids.
Checklist for titrations of acid mixtures

The following points has to be verified for successful titrations:
1. Composition: Which acids are present in the mixture?
2. Amount: How much of each acid is present in the mixture?
3. Others: Additional components?
4. pKa values: Identify the acid dissociation constants of the acid mixtures
5. Solvent: If the difference between the pKa values of the acids in the mixtures
is more than 4-5, then it may be titrated in water
- otherwise another solvent has to be used

Selected titration applications
Competence Guide
Phosphoric acid – H3PO4
Phosphoric acid H3PO4 has three hydrogen ions H+ that dissociate in water leading to increased acidity:
1. Dissociation step: H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12
2. Dissociation step: H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21
3. Dissociation step: HPO42- ⇌ H+ + PO43- pKa3 = 12.67
The strength of an acid HA is indicated by the pKa-value of its acid dissociation constant Ka, where pKa = -log(Ka).
A strong acid dissociates almost completely in water by releasing its hydrogen ions H+, thus strongly increasing
the acidity of the solution. A strong acid has a low pKa value. On the other hand, incomplete dissociation of
hydrogen ions is typical for weak acids. A weak acid has a high pKa value.
In the case of phosphoric acid, the dissociation strength i.e. the acid strength is not the same for all three hydrogen
ions. In fact, the first dissociation step has a pKa1 of 2.12, indicating a strong dissociation leading to high acidity.
The second and third dissociation steps are at pKa2 = 7.21 and pKa3 = 12.67 i.e. at pKa values typical for a
weaker dissociation and an almost vanishing dissociation, respectively. If phosphoric acid is titrated in water,
then the following titration curve is obtained:
Fig. 2: Simulated titration curve of 3 mL each of 0.1 M HCl (strong acid), 0.1 M CH3COOH (weak acid strength),
and 0.1 M NH4Cl (very weak acid) in water with 0.1 M NaOH.
The titration curve shows two equivalence points, whereas the potential jump of the third dissociation step is not
visible in aqueous solution. The first step H3PO4/H2PO4- (pKa1=2.12) corresponds to the dissociation of the first
proton, whereas the second dissociation step H2PO4-/HPO42- (pKa2=7.21) corresponds to the second proton.
The third hydrogen ion cannot be directly titrated in water. This is because the dissociation of the third step HPO42-
/PO43- is much too weak to be observed in aqueous solution i.e. the third hydrogen ion is barely dissociated in
water.

How is it possible to differentiate and determine all three dissociation steps in H 3PO4?
Competence Guide
The use of saturated sodium chloride solution as a solvent instead of water increases the ionic strength leading
to a significant shift of the pKa values, hence increasing the difference between them. The change of ionic strength
in the solvent enables to titrate all three hydrogen ions that can dissociate in the case of phosphoric acid.
This requires, two method functions TITRATION (EQP) due to the different acid strengths of the three hydrogen ions
in H3PO4: this way, the control parameters of both method functions can be optimized to the different acid
strengths. In particular, the first and second equivalence points are determined with the first TITRATION function,
whereas the third equivalence point is determined by the second TITRATION function. This is achieved by setting
suitable threshold values.
Fig. 3: Left - Titration of 0.2 g 85% H3PO4 in saturated NaCl aqueous solution with 1 M NaOH (Titration Application M202).
Right - Two TITRATION (EQP) functions with different threshold values are used in the method to recognize
all three potential jumps due to the dissociation of the three protons of phosphoric acid.

Acetic, phosphoric and nitric acid - CH3COOH : H3PO4 : HNO3
Competence Guide
The neutralization of a mixture consisting of 1 mL 1 M acetic acid (pKa=4.75), 1 mL 1 M phosphoric acid (2.12,
7.21, 12.67), and 1 mL 0.5 M nitric acid (-1.3) is performed in water.
This titration consists of four neutralization steps in water:
1) HNO3 ⇌ H+ + NO3- pKa = -1.3
2) H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12
3) CH3COOH ⇌ H+ + CH3COO- pKa = 4.75
4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21
Due to the rather small difference between the pKa values of HNO3 (pKa=-1.3) and H3PO4 (pKa1=2.12) in water,
the potential jumps at EQP of steps 1) and 2) cannot be detected.
Moreover, also the third dissociation step of phosphoric acid HPO42-/PO43- is not visible due to its extremely weak
dissociation in water. Therefore, only three potential jumps can be detected in aqueous solution:
Fig. 4: Titration of 1 mL mixture (acetic, phosphoric and nitric acid 1:1:1 v/v) with 0.1 M NaOH in water (Application M151).
The curves of HNO3 and H3PO4 can not be distinguished since their pKa-values are too close to each other.

Acetic, phosphoric, nitric acid: large excess of phosphoric acid - CH3COOH : H3PO4 : HNO3
Competence Guide
The neutralization of an acid cleaner (CH3COOH:H3PO4:HNO3, 4:23:1) can be performed in deionized water with
1 M NaOH as a titrant due to the following dissociation steps:
1) HNO3 ⇌ H+ + NO3- pKa = -1.3

1st EQP
2) H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12
3) CH3COOH ⇌ H+ + CH3COO- pKa = 4.75 2nd EQP
4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21 3rd EQP
Due to the small difference between the pKa values of HNO3 and H3PO4, the potential jumps of the first two steps
1) and 2) cannot be distinguished. Their titration curves are overlapped. Moreover, also the third dissociation
step of phosphoric acid HPO42-/PO43- is not visible due to its extremely low dissociation in water. Thus, only three
potential jumps are visible on the titration curve.
Note that the first derivative curve shows very small values i.e. approx. 2.2 and 1.8 pH/mL between 4 and 6 mL
titrant consumption. These peaks cannot be evaluated using specific threshold values since the peaks are very
small and too close to each other.
However, this can be solved by evaluating the EQPs at the corresponding potential values i.e. at potential values
QE(pH1) and QE(pH2) where pH1 = 3.75 and pH2 = 5.5. These values QE(pH) are first determined by a trial
titration. From the table of measured values the pH values corresponding to the potential jumps can be easily
determined. Note that these values depend on the concentration of the sample and on sample preparation. Thus,
it is necessary to first determine the potential values for any other mixture.
Fig. 5: Titration of 0.5 g acid cleaner (CH3COOH:H3PO4:HNO3) with 1 M NaOH in deionized water (Titration Application M152).
The evaluation at potential values pH = 3.75 and 5.5 allows for determining the content of all three acids.

Acetic, phosphoric, nitric acid: low concentrations - CH3COOH : H3PO4 : HNO3
Competence Guide
The A mixture consisting of low concentrated acids i.e. 0.1% CH3COOH, 0.25% H3PO4 and 0.1% HNO3 is
titrated in deionized water with 0.1 M NaOH due to the following dissociation steps:
1) HNO3 ⇌ H+ + NO3- pKa = -1.3

1st EQP
2) H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12
3) CH3COOH ⇌ H+ + CH3COO- pKa = 4.75 2nd EQP
4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21 3rd EQP
The pKa values of HNO3 and H3PO4 are rather close, hence steps 1) and 2) cannot be differentiated, thus only
one potential jump is visible in the curve. Also the third dissociation step of phosphoric acid HPO 42-/PO43- is not
visible due to its extremely low dissociation in water. Hence, the titration curve shows only three potential jumps.
These inflections in the titration curves are evaluated by specifying potential ranges in the calculation formula.
For this specific acid mixture, the calculations are given as it follows:
1st EQP:
HNO3 + H3PO4/H2PO4-
By subtracting the amount of H3PO4 from the first EQP the nitric acid
content can be calculated.
The amount of H3PO4 is given by the last potential jump (see picture on
next page)
2nd EQP:
CH3COOH
The amount of CH3COOH is given by the second

EQP only (see picture on next page)
3rd EQP:
H2PO4/HPO42-
The amount of H3PO4 is given by the second

dissociation step (see picture on next page).

A trial titration has to be first performed to set the optimum values for the ranges. These are identified in the table
Competence Guide
of measured values, and subsequently defined in the calculation.
Note that these values depend on the concentration of the sample and on sample preparation. Thus, it is necessary
to always first determine the potential values for any other acid mixture:
Fig. 6:
Titration of 10 mL low concentrated mixture (acetic, phosphoric, nitric acid 0.1-0.25%) with 0.1 M NaOH in water (Application M153).
The data are evaluated using potential ranges defined in the calculation formula to determine the content of each single acid component.

Sulfuric and phosphoric acids in a polishing bath – H2SO4 : H3PO4
Competence Guide
A concentrated acid mixture in a polishing bath (30% H2SO4 , 50% H3PO4, d = 1.198 g/cm3) is titrated against
0.5 M NaOH. 1 mL polishing bath is first diluted with water (1:10). 1 mL diluted solution is then added into the
beaker and further diluted with 50 mL deionized water before starting the titration with 0.5 M NaOH.
Sulfuric and phosphoric acids can dissociate two protons H+ (H2SO4) and three protons H+ (H3PO4), respectively.
Sulfuric acid is a strong acid that completely in water. The dissociation constants of H 2SO4, given as the pKa
values in water are:
1. H2SO4 ⇌ H+ + HSO4- pKa1 = -3
2. HSO4- ⇌ H+ + SO42- pKa2 = 1.92
The pKa values of H3PO4 in water are:
3. H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12
4. H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21
5. HPO42- ⇌ H+ + PO43- pKa3 = 12.67
In aqueous solution, only the first two dissociation steps of phosphoric acid are visible in a titration curve. The
third dissociation step is much too weak to be detected in water due to its pKa3 value of 12.67.
Based on the pKa values of the two acids in water, the following neutralization reactions can be given for the two
EQPs found during titration:
1st EQP: H2SO4 H2SO4 + NaOH ⇌ Na+ + HSO4- + H2O
HSO4- + NaOH ⇌ Na+ + SO42- + H2O
H3PO4 H3PO4 + NaOH ⇌ Na+ + H2PO4- + H2O
2nd EQP: H3PO4 H2PO4- + NaOH ⇌ Na+ + HPO42- + H2O
Fig. 7: Titration of 1 mL diluted bath (H2SO4/H3PO4) with 0.5 M NaOH in water (Titration Application M155).

Hydrochloric acid, acetic acid, and ammonium chloride – HCl : CH3COOH : NH4Cl
Competence Guide
The acid mixture consists of same volume amounts of 0.1 M HCl, 0.1 M CH3COOH and 0.1 M NH4Cl i.e. it
consists of a strong (HCl), weak (CH3COOH) and a very weak acid (NH4Cl). The acid mixture is titrated in
deionized water against 0.1 M NaOH.
Since HCl, CH3COOH, and NH4Cl have clearly different pKa values of -7, 4.75, and 9.25, respectively, the titration
curve shows three potential jumps in aqueous solution following their acid strength:
1st EQP: HCl + NaOH ⇌ Na+ + Cl- + H2O

2nd EQP: CH3COOH + NaOH ⇌ Na+ + HPO42- + H2O
3rd EQP: NH4Cl + NaOH ⇌ Na+ + NH3 + HPO42- + H2O
Fig. 8: Titration of an acid mixture (1 mL each of 0.1 M HCl, CH3COOH and NH4Cl) with 0.1 M NaOH in 40 mL water (Application M154).

Nitric, hydrofluoric and acetic acids in an etching bath - HNO3 : HF : CH3COOH
Competence Guide
The acid etching solution (40% HNO3 , 7% HF, and 30% CH3COOH) is titrated in a non–aqueous solvent
mixture 2-propanol:acetone 1:1 v/v against 1 M NaOH. The non-aqueous solvent allows for differentiation of the
three acids.
In fact, the pKa values in water are:
1. HNO3 ⇌ H+ + NO3- pKa = -1.3
2. HF ⇌ H+ + F- pKa = 3.18
3. CH3COOH ⇌ H+ + CH3COO- pKa = 4.75
The pKa values in aqueous solution of these acids are close to each other i.e. their difference is small – especially
for HF and CH3COOH. As a result, the titration curves in water are overlapping, and the three potential jumps of
each curve cannot be differentiated anymore.
To avoid the titration curve overlap, a bigger difference between the pKa values of these acids has to be achieved.
This is realized by diluting the sample with a non-aqueous solvent (or solvent mixture). Most suitable organic
solvents used for the titration of acids are acetone, 2-propanol (and mixtures of both), 1,2-diaminoethane and
dimethylformamide.
Based on the pKa values of the acids in water, the following neutralization reactions can be given:
1st EQP: HNO3 + NaOH ⇌ Na+ + NO3- + H2O
2nd EQP: HF + NaOH ⇌ Na+ + F- + H2O
3rd EQP: CH3COOH + NaOH ⇌ Na+ + CH3COO- + H2O
Fig. 9: Titration of 0.3 g etching solution (40% HNO3, 7% HF, and 30% CH3COOH)
with 1 M NaOH in 2-propanol:acetone 1:1 v/v.

Nitric, hydrofluoric and acetic acids in an etching bath - HNO3 : HF : CH3COOH
Competence Guide
When mixing acetic acid CH3COOH (AcOH) with hydrogen peroxide H2O2, peracetic acid CH3COOOH (PAA) is
obtained. Upon mixing the two components in aqueous solution, the following equilibrium is slowly settled:
CH3COOH + H2O2 ⇌ CH3COOOH + H2O
Note that a dilution of the mixture with water leads to a new chemical equilibrium with a lower PAA content.
The acid mixture can be titrated with a strong base such as NaOH. The difference between the pKa values of acetic
acid (pKa = 4.75) and peracetic acid (pKa = 8.2) is large enough to enable the determination of both compounds
with a single titration in aqueous solution.
If performed quickly, the dilution of the sample barely affects the equilibrium between acetic and peracetic acid,
and two potential jumps are visible in the titration curve:
1. CH3COOH ⇌ H+ + CH3COO- pKa = 4.75
2. CH3COOOH ⇌ H+ + CH3COOO- pKa = 8.2
Based on the pKa values of the acids in water, the following neutralization reactions can be given:
1st EQP: CH3COOH + NaOH ⇌ Na+ + CH3COO- + H2O
2nd EQP: CH3COOOH + NaOH ⇌ Na+ + CH3COOO- + H2O
Fig. 10: Titration of 0.25 g acid mixture (ca. 40% CH3COOH, 13% CH3COOOH) with 0.5 M NaOH (Titration Application M795).

Nitric, hydrofluoric and hexafluorotitanic acids - HNO3 : HF : H2TiF6
Competence Guide
The pickling solution HNO3/HF (e.g. 3-6 M HNO3 , 0.5-2 M HF) is used for surface treatment of titanium alloys
especially in the aeronautic industry. During pickling action hexafluorotitanic acid H 2TiF6 is formed according to
Ti + 6 HF + 4 HNO3 ⇌ H2TiF6 + 4 H2O + 4 NO2
Thus, picking titanium baths during use contain three different acids i.e. HNO3, HF and H2TiF6. These can be
titrated in pure ethanol against 0.1 M tetrabutyl ammonium hydroxide (TBAH) in 2-propanol/methanol. The use
of ethanol as a solvent allows for differentiation of the three acids since the pKa of ethanol is larger than the pKa
of water. Moreover, the precipitation of metallic hydroxides is almost suppressed1 .
Fig. 11: Titration of HNO3 – HF – H2TiF6 in ethanol with 0.1 M TBAH in 2-propanol:methanol.
Four protons H+ are titrated in total. Only three EQPs are visible since two titration curves are overlapped.
Note that the titration of this acid mixture dissolved in ethanol gives three visible potential jumps in the curve.
However, it is not possible to attribute the three potential jumps to each single involved species since H 2TiF6 has
pKa values in the same order as the ones of HNO3 and HF, respectively1. According to Cros and Bares can be
given as it follows1:
1
𝑄1 − ∙𝑄3
st
1 EQP: 𝐶(𝐻𝑁𝑂3 ) ∙ ( 4
) C(HNO3) = 63.01 g/mol
𝑚
1
𝑄2 − ∙𝑄3
nd
2 EQP: 𝐶(𝐻𝐹) ∙ ( 4
) C(HF) = 20.01 g/mol
𝑚
1 𝑄3
3rd EQP: 𝐶(𝑇𝑖) ∙ 4 ∙ C(Ti) = 47.88 g/mol
𝑚
The factor of ¼ arises from the neutralization of H2TiF6 present at the first and the second equivalence point1.
1
- B. Dustou et al., Journal of Analytical Sciences, Methods and Instrumentation, 2017, 7, 116-135.
- C. Cros, P. Bares, European Patent EP2438210A1, 2012.

Questions on acid/base titrations
Competence Guide
There are strong and weak acids – Why?

Answer: The strength of an acid is related to its dissociation in the solvent.
An acid HA dissolved in a solvent dissociates in two opposite charged particles i.e. the positively charged ion H+
(a proton), and the negatively charged anion A- . If the solvent is water H2O, the dissolution of the acid in water
can be described with the following equation:
HA + H2O ⇌ A- + H3O+
When the acid molecules HA dissociate, the H +-ions are immediately accepted by water molecules H 2O forming
H3O+ ions (hydronium ion), since H+-ions cannot exist individually in water. More precisely, the water molecules
are acting as a base, thus neutralizing the protons dissociated from the acid HA.
Note that acids never dissociate completely in the solvent i.e. the dissociation is never 100%. The degree of
dissociation i.e. the amount of released H+- ions in the solvent depends on
 the chemical structure of the acid,
and
 the ability of the solvent to accept the dissociated protons H+ i.e. its basicity.
In other words, the strength of an acid describes the extent to which it is dissociated in a given medium, and this
is quantified by determining its acid dissociation constant Ka
[𝐻3 𝑂+ ]∙[𝐴− ]
HA + H2O ⇌ H3O + +
A -
𝐾𝑎 = [𝐻𝐴]∙[𝐻2 𝑂]
A weak acid is only partially dissociated, and its dissociation constant K a is small, whereas a strong acid is
(almost) completely dissociated, hence its Ka is very large. The acid HA and its corresponding base A- form a
conjugate acid-base pair, because they are related to each other by exchange of a H +-ion.
The acid dissociation constant Ka is commonly given as the negative logarithm:
pKa = - log(Ka)
The pKa is a relevant physical-chemical parameter for the pharmaceutical industry and earth sciences, and it is
routinely determined to characterize e.g. active ingredients, raw materials and soil components.
Among other analytical techniques, the acid dissociation constant can be determined by potentiometric titration2
2
- Titration Application M760, "Determination of the Acid Dissociation Constant pKa by Potentiometric Titration"
- "Determination of the acid dissociation constant", USERCOM 1/2006, p. 9.
What is happening if an acid is dissolved in water?
Competence Guide
Answer: The acid dissociates releasing H+-ions, and the solution becomes acidic.
An acid HA dissolved in water dissociate by releasing H+-ions, which are accepted by water molecules H2O
leading to an excess of H3O+:
HA + H2O ⇌ A- + H3O+
As a result, the concentration of H3O+-ion is bigger than the one of OH--ions i.e. [H3O+] > [OH-]. In this case,
the solution is acidic, whereas the aqueous solution is basic if the opposite is valid i.e. H 3O+-concentration is
smaller than OH--concentration i.e. [H3O+] < [OH-]:
 acidic [H3O+] > [OH-]
 basic (alkaline) [H3O+] < [OH-]
The ionic product Kw = [H3O+]∙[OH-] is always constant i.e. Kw = 10-14 even when the concentrations [H3O+]
and [OH-] are very different from each other:
pH [H3O+] [OH-] Kw
0 1 0.00000000000001
1 0.1 0.0000000000001
2 0.01 0.000000000001
acidic 3 0.001 0.00000000001
4 0.0001 0.0000000001
5 0.00001 0.000000001
6 0.000001 0.00000001
neutral 7 0.0000001 0.0000001
10-14
8 0.00000001 0.000001
9 0.000000001 0.00001
10 0.0000000001 0.0001
basic
11 0.00000000001 0.001
(alkaline)
12 0.000000000001 0.01
13 0.0000000000001 0.1
14 0.00000000000001 1
The ionic product defines the extent of the pH range i.e. the extent of the acid concentration in a solvent – here:
in water. Thus, an aqueous solution
• with pH = 7 is neutral,
• it is acidic if its pH value is below 7, and

• it is basic (alkaline) if the pH is above 7.

What is happening if a base is dissolved in water?
Competence Guide
Answer: The base accepts H+-ions, and the solution becomes alkaline.
If a base B is dissolved in water, then the base molecules deprotonates H +-ions from water molecules leading to
an excess of OH-:
B + H2O ⇌ BH+ + OH-

As a result, the concentration of OH--ions is higher than the one of H3O+-ions i.e. [OH-] > [H3O+]. In this case,
the solution is basic (alkaline), and the pH value is higher than 7. In a similar way as for acid aqueous solution,
B and BH+ are a conjugate pair.
The base strength is defined following the base hydrolysis constant Kb:
[𝐻𝐵 + ]∙[𝑂𝐻 − ]
B + H2O ⇌ BH+ + OH- 𝐾𝑏 = [𝐵]∙[𝐻2 𝑂]
A weak base is a base that is only partially accepting protons H + and its base constant Kb is small. On the other
hand, a strong base has almost reacted completely with water and thus its K b constant is very large. Both
constants Ka and Kb of conjugated acid-base pairs are related to the ionic product of water Kw through the
relationship
𝐾𝑎 ∙ 𝐾𝑏 = 𝐾𝑤
In fact, HA/A- and B/BH+ (i.e. H3O+/H2O) are conjugate acid/base pairs, and thus they have the same
concentrations:
[𝐻3 𝑂+ ] ∙ [𝐴− ] [𝐻𝐵+ ] ∙ [𝑂𝐻 − ]
𝐾𝑎 ∙ 𝐾𝑏 = ∙ = [𝐻3 𝑂+ ] ∙ [𝑂𝐻 − ] = 𝐾𝑤
[𝐻𝐴] ∙ [𝐻2 𝑂] [𝐵] ∙ [𝐻2 𝑂]
Let us now consider the special case where water molecules are behaving as a base i.e. they can accept H+-
ions dissociating from an acid. In this case, then the relationship is
H2O + H2O ⇌ H3O+ + OH-
[𝐻3 𝑂+ ] ∙ [𝑂𝐻 − ]
𝐾𝑏 =
[𝐻2 𝑂] ∙ [𝐻2 𝑂]
Water is a special solvent since it can act as an acid as well as a base (amphiprotic solvent). Therefore, both
acid dissociation constant Ka and the base hydrolysis constant Kb have the same value i.e.
[𝐻3 𝑂+ ] ∙ [𝑂𝐻 − ]
𝐾𝑎 = 𝐾𝑏 =
[𝐻2 𝑂] ∙ [𝐻2 𝑂]

What about other solvents such as e.g. ethanol or methanol?
Competence Guide
Answer: Some solvents can also dissociate leading to different pH scales.
The autodissociation is not an exclusive process of water molecules, but it also takes place in other solvents.
Similarly to water, there are solvents such as methanol or acetic acid that also dissociate and release H +-ions in
solution (protic solvents), as well as other solvents that can only react as a base by accepting a H+-ion.
This means that non-aqueous solvents can be also classified as acids and bases, and thus it is possible to
calculate the acid dissociation constant Ka as well as the base constant Kb, respectively. In fact, each solvent HS
has its characteristic autodissociation which is described by its specific ionic product KHS = [H+]∙[S-]:
Autodissociation: HS + HS ⇌ H2S+ + S-
KHS = [H2S+]∙[S-] pKHS = -log(KHS)
Hence, each non-aqueous solvent HS has a different pH scale according to its pKHS-value:
Methanol: CH3OH + CH3OH ⇌ CH3OH2+ + CH3O-

KHS = 10-16.7 pKHS = 16.7
Acetic acid: CH3COOH + CH3COOH ⇌ CH3COOH2+ + CH3COO-

KHS = 10-14.9 pKHS = 14.9
Note that non-aqueous solvents with autodissociation constants KHS smaller than that of water KW have a larger
pH scale i.e. their pH scales are extended over the range 0-14. This is shown in the following figure:
Fig. 12: pH scales of different solvents.
The acidic cations HS2+ e.g. CH3OH2+ and CH3COOH2+ can be also sensed by the pH glass electrode, indeed.
Thus, the pH sensor can measure over a bigger range of potentials than in water. This allows for the content
determination of broader range of acids (bases) by potentiometric titrations i.e. of acids (bases) whose measured
potentials are outside the range of aqueous solutions (pH range 0-14).

Why do we titrate acid or bases in non-aqueous solvents?
Competence Guide
Answer: Titration in non-aqueous solvents allows improving the potential jump and the
profile of titration curves.
Samples can be also dissolved in non-aqueous solvents to achieve complete dissolution and more pronounced
potential jumps in the titration curves. In fact, the condition for a straightforward recognition and evaluation of the
inflection point in the S-shaped titration curve by the titration instrument is a big, steep and clear potential jump.
Moreover, a differentiation of each single acid in a mixture can be achieved when titrating in non-aqueous
solvents. Through suitable selection of the solvent, the titration of an acid mixture lead to a curve showing several
potential jumps corresponding to the acidic components.
In water, all strong acids HA react with water molecules to form the acid H 3O+ and the conjugate base A- , and
the formed H3O+ is the strongest acid existing in aqueous solutions. All acids HA tend to become indistinguishable
in strength when dissolved in strongly basic solvents due to the greater affinity of strong bases for dissociated H +-
ions3 . In other words: the strength of a strong acid is reduced and limited ("leveled") by the basicity of water.
For instance, perchloric HClO4 is a stronger acid than hydrochloric acid HCl in water. They both dissociate H +-
ions which are accepted by water molecules H2O forming H3O+ since they both are stronger acids than H3O+-
ions. For this reason, these acids appear to be equally strong in water i.e. both acids are leveled to H3O+-ions in
water (leveling effect):
HClO4 + H2O ⇌ H3O+ + ClO4-
HCl + H2O ⇌ H3O+ + Cl-
Thus, when titrating a HClO4/HCl aqueous solution with KOH or NaOH as a titrant, only the formed H 3O+ is
neutralized by the alkaline titrant: it seems that both acids have the same strength in water. Hence, it is not
possible to differentiate the equivalence points of both acids, and only one equivalence point (neutralization of
H3O+) will be visible in the titration curve.
The situation completely changes when this acid mixture is dissolved in pure (glacial) acetic acid CH 3COOH.
Water and acetic acid have similar autodissociation constant 4. However, strong aqueous acids such as HClO 4
and HCl dissociate only to different degrees in acetic acid i.e. HClO4 and HCl have different strengths in acetic
acid. Such a solvent is then indicated as differentiating solvent.
Acetic acid is a weaker base compared to water, and thus it is a weaker H +-ion acceptor than water5. Because
of the different acidic strengths of HClO4 and HCl, the corresponding titration curve shows two distinct
equivalence points in acetic acid:
HClO4 + CH3COOH ⇌ CH3COOH2+ + ClO4-
HCl + CH3COOH ⇌ CH3COOH2+ + Cl-
For this reason, a useful rule to estimate if acids in a mixture can be differentiated is to evaluate their pKa-
values: if they are too close to each other, then the titration curve will overlap and no differentiation is possible.
3
Wikipedia, "Leveling effect", https://en.wikipedia.org/wiki/Leveling_effect , recalled on 6.11.2020.
4
E.P. Serjeant, "Potentiometry and Potentiometric Titrations", Chemical Analysis Volume No. 69, John Wiley & Sons, 1984, p.367.
5
Wikipedia, "Leveling effect", https://en.wikipedia.org/wiki/Leveling_effect , recalled on 6.11.2020.

What about solvents that do not dissociate?
Competence Guide
Answer: Solvents like acetone and toluene can also be used as differentiating solvents
in titration of acid mixtures.
Beside non-aqueous solvents showing self-dissociation such as e.g. acetic acid or methanol and thus behaving
as acids and bases (amphiprotic solvents), there are also non-aqueous solvents commonly used in titration that
neither dissociate nor accept H+-ion (aprotic solvents). Hence, they do not interact with acids or bases, or the
interaction is negligible compared to amphiprotic solvents such as methanol and water.
This can be understood by taking into account their relative permittivity εr (obsolete: dielectric constant). In fact,
the permittivity is a physical parameter in electromagnetism that allows characterizing the solvent behavior. The
permittivity is a proportionality constant that gives an estimation of the electric polarizability of a substance in an
electric field6. More accurately, it gives an indication on the distribution of electrical charges of a medium in an
electric field. Briefly, the higher the permittivity, the stronger will be the distribution of electrical charges leading to
a strong polarization:
Solvent Rel. permittivity εr 7

8
Water H2O 78.3
Methanol CH3-OH 32.6
Ethanol CH3-CH2-OH 24.3
Acetone CH3-CO-CH3 20.7
2-Propanol CH3-COH-CH3 18.3

A dielectric medium showing orientation of
charged particles creating polarization effects.
Such a medium can have a lower ratio of
Acetic acid CH3-COOH 6.20
electric flux to charge (more permittivity) than
empty space 6 Chlorobenzene C6H5-Cl 5.61
Tab. 3: Chloroform CHCl3 4.81
Relative permittivity of different
Toluene C6H5-CH3 2.38
solvents used in titration.
Benzene C6H6 2.27
The permittivity ε of aprotic solvents e.g. acetone and toluene is lower than the one of water (rel. permittivity εr =
78.3 at 25 °C), and for this reason these solvents are added to titration solutions consisting of amphiprotic
solvents (e.g. ethanol, methanol and 2-propanol) to modify the permittivity.
In fact, the addition of aprotic, miscible solvents improves the quality of the potential jump in the region close to
the equivalence point i.e. to get a more pronounced and higher jump 8 for a better evaluation of the measured
curve by the titrator.
Acetone, chloroform, toluene and benzene represent well-known aprotic solvents used in titration. For instance,
toluene is commonly used pure or in combination with other solvents to achieve a complete dissolution of mineral
oils petroleum products before titration.
6
https://en.wikipedia.org/wiki/Permittivity , 09.11.2020. (http://hyperphysics.phy-astr.gsu.edu/hbase/electric/dielec.html#c1 , Public Domain, https://commons.wikimedia.org/w/index.php?curid=37665552)
7
https://depts.washington.edu/eooptic/linkfiles/dielectric_chart%5b1%5d.pdf , University of Washington, Dept. of Chemistry, Prof. Dalton's Research Group, 09.11.2020.
8
E.P. Serjeant, "Potentiometry and Potentiometric Titrations", Chemical Analysis Volume No. 69, John Wiley & Sons, 1984, p.368-371.

Non-aqueous acid/base titrations of mixtures
Competence Guide
The following paragraphs are an excerpt from the brochure "Titration in non-aqueous solutions" published in
1995 by Riedel-de Haën (Now: Honeywell) 9. This booklet of approx. 30 pages is a very useful guideline that
support the users with practical recommendations when performing non-aqueous titrations. The theory presented
in this brochure is based on the literature of I. Gyenes, E.P. Serjeant, J. S. Fritz and W. Huber cited in the last
chapter of this document on page 34.
Unfortunately, this brochure is not available anymore, hence the chance of losing such a helpful knowledge source
is very high, and this would be clearly a pity. To avoid this loss, the relevant information on non-aqueous titrations
out of this booklet have been included in this guide on titration of acid mixtures.
Key points and motivation

Non-aqueous titrations extends the application range of common classical titrations:
1. Broader application range

Titrations in organic solvents allow to determine the content of very weak bases and acids that cannot be
analyzed in aqueous solution:
2. Differentiation of acid mixtures

Acid mixtures whose acids have pKa values close to each other and thus cannot be differentiated in
aqueous medium may be successfully titrated in selected non-aqueous solvents such as e.g. acetone and
isopropanol.
3. Extension of solubility range

Organic solvents extend the solubility range. In fact, many substances and compounds that are partially (or
completely) insoluble in water can be dissolved in organic solvents, and thus they can be now titrated
Since non-aqueous solvents generally have a high thermal expansion coefficient compared to water e.g. ten times
more, the laboratory temperature should be kept constant to reduce errors during titration. In fact, a temperature
difference of 1°C only may lead to a result deviation of 0.2% when using organic solvents in titration.
9
According to Honeywell, there is no author and no copyright for this brochure "Titration in non-aqueous solutions" since it was developed by technical and marketing departments based on the
scientific literature presented in the last chapter "Literature" of this document (Personal communication with Honeywell, November 2020).

Titration of acids and acid mixtures in non-aqueous solutions
Competence Guide
In aqueous solutions, only soluble acids having a pKa value up to 7 can be titrated. Weaker acids with pKa values
up to 12 can be titrated in organic solvents. In general, these titrations in organic solvents are performed using
0.1 M tetramethylammonium hydroxide (TMAH) or tetra-n-butylammonium hydroxide (TBAH).
When titrating acid mixtures, the choice of the appropriate solvent is crucial to achieve correct results. The
following table gives an overview of the most commonly used solvents for acid content determination in non-
aqueous solution:
Organic solvents
Comments
for acids/acid mixtures
1,2-Diaminoethane − It allows for titration of acids with a pKa value up to 11.

(Ethylenediamine) − Stronger acids are leveled, and for pKa < 6 the differentiation of acids in a
H2N-CH2-CH2-NH2 mixture is not possible.
− This solvent must be protected from CO2-intake from air by means of CO2
absorbing material.
− Its odor is unpleasant, work in a fume-hood.
Pyridine − It shows a similar behavior as 1,2-diaminoethane.

C 5H5N − The potential jumps at the equivalence points are more pronounced than in
1,2-diaminoethane.
− Acids with pKa < 3 are leveled.
− Caution: Pyridine is toxic. Wear gloves, lab coat, safety goggles and work
in a fume-hood.
− Protect from CO2-intake from air.
Dimethylformamide − Excellent solvent for salts and good solvent for the titration of acids and acid
(DMF, N,N-Dimethylamide) mixtures.
OHC-N-(CH3)2 − DMF allows for better differentiation of acid components in a mixture with
respect to pyridine.
− The potential jumps are very well pronounced.
− Only strong acids with pKa ≤ 0 are leveled.
− The CO2 absorption is less pronounced than in pyridine due to the lower
basicity.
− Not very stable:
DMF can be hydrolyzed by strong acids if it is kept for a long time in acidic
solutions.
2-Propanol − It is a good solvents for acids and acid mixtures.

− Titrations in 2-propanol allow for differentiation of acid components up to
pKa = 0.
− 2-Propanol is less suitable as a solvent for very weak acids i.e. from pKa =
11 upwards.
Acetone − It is the ideal solvent for differentiation of acid mixtures.

Even perchloric and hydrochloric can be differentiated in acetone.
Other solvents − Methanol or ethanol are used to determine the first dissociation step of
dicarboxylic acids.
− Tert-butanol is a good solvent for the determination of very weak acids.
− Methylethylketone is a good solvent to differentiate strong acids.

The following figures illustrate the titration of acids in dimethylformide DMF (fig. 12) and acetone (fig. 13).
Competence Guide
Depending on the selected solvent, the potential jumps are more or less pronounced, thus it facilitates the
recognition of the equivalence point.
Fig. 13: Titration of different acids in dimethylformamide (DMF)

against 0.1 M tetramethylammonium hydroxide (TMAH) in 2-propanol with 2% water.
Fig. 14: Titration of different acids in acetone against 0.1 M TMAH in 2-propanol with 2% water.

The choice of the appropriate solvent for differentiation in acid mixtures is crucial for carrying out a successful
Competence Guide
titration. Beside this, the appropriate alkaline titrant has to be selected to achieve accurate and precise results. In
general, strong bases such as TMAH and TBAH are needed for the titration of acids in non-aqueous solvents:
Alkaline titrants
Comments
for acids/acidic mixtures
− It is sufficiently soluble in polar organic solvents.
− The stability of TMAH titrant solutions is limited since TMAH
decomposes forming trimethylamine and methanol.
− Methanolic TMAH-solutions are relatively stable. However, due to the
leveling action of methanol their use is limited extent.
Tetramethylammonium hydroxide − A 2-propanol TMAH-solution is preferable because the leveling action
of 2-propanol is less pronounced than methanol. This is a big
(TMAH)
advantage when titrating very weak acids such as e.g. phenol.
− Propanol/methanol mixtures are used instead of pure methanolic
solutions since they lead to a good compromise between storage
stability and titration properties.
− Low water contents in the range of 1% increase stability, and
improve conductivity without affecting the titration properties.
− Under these conditions 0.1 M TMAH can be used for ca. one year.
− TBAH shows the same basicity as TMAH during titration. However,

tetrabutylammonium salts are generally more soluble.
Tetrabutylammonium hydroxide
− On the other hand, some tetramethylammonium salts are sparingly
(TBAH) soluble and can form a layer on the electrodes.
− TBAH has a shorter lifetime.
The following figure illustrates the effects of methanol addition in the titrant on the titration curve:
Fig. 15: Titration of phenol in dimethylformamide (DMF).

There are several points to be considered when working with these titrants:
Competence Guide
 Strong bases such as TMAH and TBAH easily absorb CO2 from the air. This leads to the formation of the
weak base tetraalkylammonium carbonate. Thus, the titrant bottle must be protected using CO2-
absorbing material i.e. sodium hydroxide on support to suppress the formation of this impurity.
 Quaternary ammonium hydroxides such as TMAH and TBAH also have limited shelf life due to the
gradual decomposition to a trialkylamine, an additional impurity. The latter is a weaker base than the
corresponding tetraalkylammonium hydroxide, and it also affects the titration result when using old
TMAH/TBAH titrant solutions.
 To test for impurities i.e. tertiary amine and carbonate, TMAH and TBAH can be titrated in acetone with
perchloric acid. Both impurities are visible in the titration curve as clear potential jumps:
Fig. 16: Titration of TMAH in acetone containing the impurities CO2 and trimethylamine (TMA)
using 0.1 M perchloric acid in 2-propanol as a titrant.
The bases are neutralized according to their base strengths:
 first, the strongest base i.e. TMAH is titrated by neutralization of the released hydroxide ion.
 Subsequently, CO2/carbonate is titrated leading to the second equivalence point.
 Finally, the weakest base i.e. trimethylamine TMA is neutralized by perchloric acid to the third equivalence
point.

 The following figure shows the interference of different amount of trimethylamine TMA on the titration of
Competence Guide
acids in acetone with a basic TMAH/TMA solution:
Fig. 17: Titration of different acids in acetone. The titrant is a mixture of

0.1 M tetramethylammonium hydroxide and 0.02 M trimethylamine in 2-propanol.
Note that during the titration of the weakest acids phenol and nitrophenol (see curves 1 and 2) TMA does not
react at all with the acids i.e. the second equivalence point (EQP) is not visible. This due to the fact that TMA is a
much weaker base than TMAH.
However, with increasing acid strengths (see curves 5-7), two equivalence points appear in the curves:
 The first EQP is due to the neutralization of both TMAH and TMA by the strong acid, whereas
 the second EQP is due to neutralization by TMAH only. In fact, as long as there is an excess of strong
acid in the sample solution, both bases TMAH and TMA are neutralized:
1st EQP: HX + (CH3)4NOH ⇌ (CH3)4NX + H2O
HX + (CH3)3N ⇌ (CH3)3N∙HX
2nd EQP: (CH3)3N∙HX + (CH3)4NOH ⇌ (CH3)3N + (CH3)4NX + H2O
If the acids are dissolved in less differentiating solvents such as diaminomethane or pyridine, the first EQP cannot
be measured. The first EQP is more pronounced when using stronger differentiating solvents.

• A similar behavior can be observed when carbon dioxide is absorbed from the air, which reacts to
Competence Guide
carbonates in an alkaline solution. Since tetraalkylammonium carbonate is a stronger base than the
tertiary amine, the first EQP is shifted into the more basic range i.e. to lower potential values:
Fig. 18: Titration of different acids in acetone. The titrant is a mixture of

0.1 M tetramethylammonium hydroxide and 0.02 M CO2 in 2-propanol.
The corresponding neutralization reactions for both equivalence points are given below:
1st EQP: HX + (CH3)4NOH → (CH3)4NX + H2O
2 HX + ((CH3)4N)2CO3 → 2 (CH3)4NX + CO2 + H2O
2nd EQP: CO2 + 2 (CH3)4NOH → ((CH3)4N)2CO3 + H2O
However, the second EQP may not be quantitatively evaluated since CO 2 can partly escape from the
sample solution.

Titration of bases in non-aqueous solutions
Competence Guide
In aqueous solutions, only strong bases having a pKb value up to 7 can be titrated, e.g. aliphatic amines. Weaker
bases such as aromatic amines or heterocycles with pKb up to 12 can be titrated in organic solvents e.g. in
glacial acetic acid with perchloric acid in glacial acetic acid as a titrant:
Fig. 19: Non-aqueous titration of bases with increasing base strength (i.e. decreasing pKb values) using
0.1 M perchloric acid in acetic acid. The samples are also dissolved in glacial (= pure) acetic acid.
Mixtures of bases can be analyzed by a single titration through differentiation of the corresponding equivalence
points in the titration curve. The differentiation leads to different potential jumps that can be easily evaluated. As
in the case of acid mixtures, this can be achieved by selecting a suitable organic solvent.
By using organic solvents such as acetone, dioxane and mixtures thereof, it is possible to modify the strength of
the bases to improve the potential jump at the inflection point of the titration curve. The following diagram illustrates
the effect of different bases on the potential jumps:
Fig. 20: Titration of bases in acetone with 0.1 M perchloric acid in dioxane.
In figure 19, the effect of acetone on the basicity is clearly visible in the region of the inflection point: strong bases
show a pronounced S-shaped profile with a large potential jump, whereas weak bases exhibit a flat curve with
small potential jumps. The effect is very pronounced for TMAH (curve 6), leading to a considerable increase of its
basicity as indicated by the high potential jump of more than 1000 mV.

Figure 20 illustrates the titration of the two bases N-ethylpiperidine (pKb = 3.59) and pyrazole (pKb = 11.51) in
Competence Guide
acetone. The sample is titrated with perchloric acid dissolved in dioxane with 0.5% water. The differentiation of
the bases leads to two clear potential jumps at the first and second equivalence points in the titration curve:
Sample: Solution containing N-ethylpiperidine and pyrazole

Titrant: 0.1 M perchloric acid in dioxane with 0.5% water
Solvent: Acetone
Fig. 21: Titration of two bases in acetone with 0.1 M HClO4 in dioxane with 0.5% water (1 = N-ethylpiperidine , 2 = Pyrazole).
If the water content of the titrant is increased, then the second equivalence point is not visible anymore.
The last example is concerned with the titration of a basic mixture with perchloric acid in 2-propanol. Both bases
iso-propylamine (pKb = 3.37) and aniline (pKb = 9.42) are dissolved in acetone:
Sample: Solution containing iso-propylamine and aniline.

Titrant: 0.1 M perchloric acid in 2-propanol
Solvent: Acetone
Fig. 22: Titration of iso-propylamine and aniline in acetone with 0.1 M HClO4 in 2-propanol (1=Iso-propylamine , 2=Aniline).
With respect to the previous titration, note that the potential jumps are smaller and not so pronounced anymore.
This is due to the fact that 2-propanol is a more polar solvent than dioxane. Nevertheless, the second potential
jump due to aniline is still visible since aniline (pKb = 9.42) is a stronger base than pyrazole (pKb = 9.42).

An overview of the most common organic solvents as well as of the titrants used for simultaneous titrations of
Competence Guide
bases in a mixture is summarized in the following table:
Solvents for
Comments
base/alkaline mixtures
- Acetic acid is the most commonly used solvent. It has good
dissolution properties for most bases, provides pronounced potential
Acetic acid curves, sharp end points and also enables titration of weak bases up
to pKb = 12.
- Acetylations may take place, e.g. in the case of aromatic amines.
- Acetic acid anhydride has a similar behavior as acetic acid but it is
the solvent to be preferred for weak bases (pKb≥10-12) as it is
Acetic acid anhydride anhydrous.
- Primary and secondary amines cannot be titrated as they are
acetylated.
- 2-Propanol is a good solvent due to its relatively high dielectric
constant and low intrinsic acidity.
2-Propanol
- In general, 2-propanol differentiates well However, it is not
recommended for the titration of weak bases (pKb > 10-12).
- Acetone is frequently used because it enables very good differentiation
Acetone
(see fig. 2) of bases and still has adequate dissolving properties.
Methylisobutylketone - These solvents can be also used as pure solvent or in mixture since
Tert-butanol, Diethyl ether they lead good titration curves.
Glycol/chloroform mixture
Acid titrants for

Comments
mixtures of bases
- Perchloric acid is used almost exclusively for titration.
Perchloric acid
- If the solvent is glacial acetic acid, 0.1 M perchloric acid in acetic acid
in glacial acetic acid
is used as a titrant due to its stability for storage.
- When working with differentiating solvents such as acetone or 2-
propanol, acetic acid interferes because of its leveling effect.
Perchloric acid - In this case, 0.1 M perchloric acid in dioxane is recommended.
in acetone
- 0.1 M perchloric acid in dioxane has a limited lifetime. It must always
or be prepared freshly. In fact, with time it gradually turns to brown due to
in 2-propanol decomposition.
or - 0.1 M perchloric acid in 2-propanol is the most used titrant. It has an
in dioxane unlimited lifetime and gives very comparable results as with dioxane.
However, for weak bases with pKb > 10, the use of 2-propanol is not
recommended.

Literature
Competence Guide
István Gyenes,
"Titration in non-aqueous media",
Iliffe Books Ltd., London, England, U.S. Publisher: D. Van Nostrand Co., 1968.
E.P. Serjeant,
"Potentiometry and Potentiometric Titrations",
Chemical Analysis Volume No. 69, John Wiley & Sons, 1984.
James S. Fritz,
"Acid-Base Titrations in Non-Aqueous Solvents",

Allyn and Bacon Inc., Boston, 1973.
Walter Huber,
"Titrationen in nichtwässrigen Lösungsmitteln",
in "Methoden der Analyse in der Chemie", edited by F. Hecht, R. Kaiser and H. Kriegsmann,
Band 1, Akademische Verlagsgesellschaft, Frankfurt/Main 1964.

This application bulletin represents selected, possible application examples.
These have been tested with all possible care in our lab with the analytical
instrument mentioned in the bulletin. The experiments were conducted and the
resulting data evaluated based on our current state of knowledge.
However, the application bulletin does not absolve you from personally testing
its suitability for your intended methods, instruments and purposes. As the use
and transfer of an application example are beyond our control, we cannot
accept responsibility therefore.
When chemicals and solvents are used, the general safety rules
and the directions of the producer must be observed.
Titration Guide
Simultaneous Determination of Acid Contents in Mixtures
This Titration Guide covers selected applications and background

information for the simultaneous titration of acid components in
acid mixtures with Titration Excellence T5, T7 and T9.
First, the results for typical acid mixtures such as HCl/HNO3 and
CH3COOH/H3PO4/HNO3 are presented. Subsequently, relevant
background information is presented by means of frequently asked
questions. The Guide is completed with basic theory on acids and
bases in aqueous and non-aqueous solvents.
The applications have been developed by the Market Support Group

Analytical Chemistry. They are available from the Applications
Library on the METTLER TOLEDO website www.mt.com.
www.mt.com
For more information
Mettler-Toledo GmbH, Analytical

Heuwinkelstrasse 3
CH-8606 Nänikon, Switzerland
Tel +41-44 944 22 11
Fax +41-44 944 30 60
Subject to technical changes without notice.

©12/2020 Mettler-Toledo GmbH, 30651782
Market Support Group Analytical Chemistry

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Competence Guide

Titration of Acid Mixtures

Daniel Buchmann Dr. Cosimo A. De Caro

METTLER TOLEDO Page 1 of 34

SELECTED TITRATION APPLICATIONS 7

QUESTIONS ON ACID/BASE TITRATIONS 18

NON-AQUEOUS ACID/BASE TITRATIONS OF MIXTURES 24

METTLER TOLEDO Page 2 of 34

Titration: What is it?

Titration of acid mixtures

METTLER TOLEDO Page 3 of 34

How do we know which potential jump corresponds to which acid?

HCl CH3COOH NH4Cl

Acid dissociation constant – pKa

H2C2O4 (Oxalic acid) 1.25 * pKa1

H3PO4 2.12 pKa1

CH3COOH (Acetic acid) 4.75

CH3COOOH (Peracetic acid) 8.2 *

NH4Cl (Ammonium chloride) 9.24 *

Tab. 1: Acid strength of selected acids:

METTLER TOLEDO Page 4 of 34

METTLER TOLEDO Page 5 of 34

Acid mixtures / Polyprotic acids Titration Solution

H3PO4 Titration to 3 EQPs - Sample dissolved in saturated NaCl solution

HNO3 : HF : CH3COOH Differentiation - Sample dissolved in acetone:2-propanol 1:1

Tab. 2: Simultaneous titrations of acid mixtures and of polyprotic acids.

Checklist for titrations of acid mixtures

METTLER TOLEDO Page 6 of 34

1. Dissociation step: H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12

2. Dissociation step: H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21

3. Dissociation step: HPO42- ⇌ H+ + PO43- pKa3 = 12.67

METTLER TOLEDO Page 7 of 34

METTLER TOLEDO Page 8 of 34

This titration consists of four neutralization steps in water:

1) HNO3 ⇌ H+ + NO3- pKa = -1.3

2) H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12

3) CH3COOH ⇌ H+ + CH3COO- pKa = 4.75

4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21

METTLER TOLEDO Page 9 of 34

1) HNO3 ⇌ H+ + NO3- pKa = -1.3

4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21 3rd EQP

METTLER TOLEDO Page 10 of 34

1) HNO3 ⇌ H+ + NO3- pKa = -1.3

4) H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21 3rd EQP

The amount of CH3COOH is given by the second

The amount of H3PO4 is given by the second

METTLER TOLEDO Page 11 of 34

of measured values, and subsequently defined in the calculation.

METTLER TOLEDO Page 12 of 34

1. H2SO4 ⇌ H+ + HSO4- pKa1 = -3

2. HSO4- ⇌ H+ + SO42- pKa2 = 1.92

The pKa values of H3PO4 in water are:

3. H3PO4 ⇌ H+ + H2PO4- pKa1 = 2.12

4. H2PO4- ⇌ H+ + HPO42- pKa2 = 7.21

5. HPO42- ⇌ H+ + PO43- pKa3 = 12.67

HSO4- + NaOH ⇌ Na+ + SO42- + H2O

H3PO4 H3PO4 + NaOH ⇌ Na+ + H2PO4- + H2O

2nd EQP: H3PO4 H2PO4- + NaOH ⇌ Na+ + HPO42- + H2O

METTLER TOLEDO Page 13 of 34

1st EQP: HCl + NaOH ⇌ Na+ + Cl- + H2O

3rd EQP: NH4Cl + NaOH ⇌ Na+ + NH3 + HPO42- + H2O

METTLER TOLEDO Page 14 of 34

In fact, the pKa values in water are:

1. HNO3 ⇌ H+ + NO3- pKa = -1.3