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Titration is an analytical technique which allows the quantitative determination of a specific substance
(analyte) dissolved in a sample. It is based on a complete chemical reaction between the analyte and a
reagent (titrant) of known concentration which is added to the sample:
Analyte + Reagent(Titrant) -> Reaction Products
The titrant is added until the reaction is complete. In order to be suitable for a determination, the end of the
titration reaction has to be easily observable. This means that the reaction has to be monitored (indicated)
by appropriate techniques, e.g. potentiometry (potential measurement with a sensor) or with colour
indicators. The measurement of the dispensed titrant volume allows the calculation of the analyte content
based on the stoichiometry of the chemical reaction. The reaction involved in a titration must be fast,
complete, unambiguous and observable.
A well-known example is the titration of acetic acid in vinegar with sodium hydroxide.
What are the advantages of titration?
+ Classical, well-known analytical technique
+ Fast
+ Very accurate and precise technique
+ High degree of automation
+ Good price/performance ratio compared to more sophisticated techniques
+ It can be used by low-skilled and trained operators
+ No need for highly specialised chemical knowledge
In which industries or segments is titration used?
A non-comprehensive listing of industries using titration:
Car Manufacturing, Ceramics, Chemical industry, Coal products, Coating, Cosmetics
Detergents
Electronic, Electroplating, Energy, Explosives
Food
Glass, Government
Health
Leather
Machinery
Packing materials, Paints, Pigments, Paper&Pulp, Petroleum, Pharmaceuticals, Photo, Plastic products,
Printing & Publishing
Rail, Rubber
Stone (Clay, Cement)
Textile, Tobacco
Water
Zeolite
What is an autotitrator?
Automated titrators are microprocessor-controlled instruments which allow the automation of all operations
involved in titration:
1. Titrant addition
2. Monitoring of the reaction (Signal acquisition)
3. Recognition of the endpoint
4. Data storage
5. Calculation
6. Results storage
7. Transfer of data to printer or computer/external system
How does an autotitrator work?
Automated titrators follow a defined sequence of operations. This sequence is basically the same for all
different models and brands. It is performed and repeated several times until the endpoint or the
equivalence point of the titration reaction is reached (titration cycle). The titration cycle consists mainly of 4
steps:
1. Titrant addition
2. Titration reaction
3. Signal acquisition
4. Evaluation
Each step has different specific parameters (e.g. increment size) which have to be defined according to the
specific titration application. More complex applications require more steps, e.g. dispensing of an additional
reagent for back titrations, dilution, adjusting of the pH value. These steps and the corresponding
parameters are resumed in a titration method.
What is the historical development of autotitrators?
The classical way:
Titration is a classical analytical technique widely used. Originally, it was performed by adding the titrant
using a graduated glass cylinder (burette). With a tap the titrant addition was regulated manually. A change
in colour indicated the end of the titration reaction (endpoint). At first, only those titrations showing a
significant colour change upon reaching the endpoint were performed. Later titrations were coloured
artificially with an indicator dye. The precision achieved depended mainly on the chemist's skills and, in
particular, on his different colour perception.The modern way:
Titration has experienced a strong development: manual and -later- motorized piston burettes allow
reproducible and accurate titrant addition. Electrodes for potential measurement replace the colour
indicators, achieving higher precision and accuracy of the results. Graphical plot of potential versus titrant
volume allows a more exact statement about the reaction than the colour change at the endpoint. With
microprocessors the titration can be controlled and evaluated automatically. This represents a relevant step
towards complete automation.
Today and tomorrow:
Developmentis not yet complete. Modern autotitrators allow the definition of complete analysis sequences
achieving maximum flexibility in method development. For each application the specific method can be
defined by combining simple operation functions like "Dose", "Stir", "Titrate", "Calculate" in a defined
sequence. Auxiliary instruments (sample changers, pumps) help in reducing and simplifying the work load in
laboratories. A further trend is the connection to computers and Laboratory Information Management
Systems (LIMS).
Which types of chemical reactions are used in titration?
There are several assay reactions which are used in titration:
Acid/Base reactions:
Examples: Acid content in wine, milk. Acid content in ketchup. Content of inorganic acids like sulfuric acid.
Precipitation reactions:
Examples: Salt content in crisps, ketchup and food; Silver content in coins,
Sulfate content in mineral water; Sulfate content in electroplating bath
Redox reactions:
Examples: Content of copper, chromium and nickel in electroplating baths
Complexometric reactions:
Examples: Total hardness of water (Mg and Ca); Calcium content in milk and cheese; Cement analysis
Colloidalprecipitation reaction:
Examples: Anionic surfactant content in detergents; Anionic surfactant content in washing powders; Anionic
surfactant content in liquid cleanser.
What are the indication methods used in titration?
Titrations can be classified according to the indication principles and the chemical reaction occurring:
Potentiometry:
The concentration-dependent potential (mV) of a solution is measured against a reference potential.
Examples: Acid/Base (aqueous/non-aqueous), redox, precipitation reactions.
Voltametry:
The concentration-dependent potential of a solution (mV) is measured at a constant polarizing electric
current.
Examples: Karl Fischer water determination.
Amperometry:
The current flowing in a sample solution (A) is measured at a constant polarizing potential.
Examples: Iron(II) and Vitamin C determination.
Photometry:
The light transmission (mV or % transmission) of a coloured or turbid solution is measured with a
photometric sensor.
Examples: Complexometric and turbidimetric reactions.
Conductivity:
The conductivity of a solution (S/cm) is measured by a conductivity meter.
Example: Alpha acids in beer.
Thermometry:
The temperature of a sample is measured by a temperature sensor.
Example: Boric acid content.
What is titration?
Titration is an analytical technique which allows the quantitative determination of a specific substance
(analyte) dissolved in a sample. It is based on a complete chemical reaction between the analyte and a
reagent (titrant) of known concentration which is added to the sample:
Analyte + Reagent(Titrant) -> Reaction Products
The titrant is added until the reaction is complete. In order to be suitable for a determination, the end of the
titration reaction has to be easily observable. This means that the reaction has to be monitored (indicated)
by appropriate techniques, e.g. potentiometry (potential measurement with a sensor) or with colour
indicators. The measurement of the dispensed titrant volume allows the calculation of the analyte content
based on the stoichiometry of the chemical reaction. The reaction involved in a titration must be fast,
complete, unambiguous and observable.
A well-known example is the titration of acetic acid in vinegar with sodium hydroxide.
Thermometry:
The temperature of a sample is measured by a temperature sensor.
Example: Boric acid content.
What is the difference between the symmetric and the asymmetric evaluation principle?
Symmetric curve:
The curve has a symmetric profile and the equivalence point is the inflection point of the curve.
This curve is evaluated by plotting the first derivative dE/dV versus titrant consumption V. The maximum of
the derivative is at the inflection point and indicates the equivalence point.
For the automatic evaluation of the symmetric S-curve the titrator provides the appropriate procedure
("STANDARD").
Examples: Acid/base titrations, redox titrations, precipitation titrations
Asymmetric curve:
This titration curve shows a different profile than the typical symmetric S-curve, and thus a different
evaluation procedure is needed. This is based on the Tubbs procedure (see "Fundamentals of titration", ME704153).
The asymmetry has to be taken into account for curve evaluation. The equivalence point is shifted towards
the region with the stronger curvature.
The curve is fitted with two circles (better: two hyperbolas). The intersection point of the line connecting the
two foci and the titration curve indicates the equivalence point.
Examples: Photometric titrations, redox titrations, turbidimetric titrations
Are there other evaluation principles used in the titrator?
Four different curves can be observed and evaluated with the corresponding procedures specified in the
titration method.
Symmetric curve (see answer above)
Asmmetric curve (see answer above)
Minimum (Maximum) curve:
This curve shows the typical profile obtained from turbidimetric titrations, e.g., determination of the anionic
surfactant content, where a colloidal precipitate is formed by adding the titrant. This leads to an increased
turbidity of the solution. The profile of the curve is characterized by a minimum in the curve which indicates
the equivalence point EQP. The precipitate formation is monitored with a photometric sensor, and the light
transmission in the solution is measured with a phototrode. At the equivalence point, the turbidity reaches its
maximum, i.e. the transmission has a minimum. A special evaluation procedure allows the determination of
the minimum of the curve ("MINIMUM"). Curves showing a maximum are evaluated with the procedure
"MAXIMUM". Example: Content determination of anionic surfactants in cooling lubricants.
Examples: Ionic surfactant determination (turbidimetric titrations).
Segmented curve:
The profile of this curve shows a clear bend at the equivalence point. This profile is obtained when
conductometric titrations are performed (notice the unit of measurement in the graphical representation:
S/cm, micro-Siemens). The EQP is defined by a sharp change in conductivity. The curve is evaluated by
determining the maximum of its second derivative.
Examples: alpha-Acids in beer (conductometric titration), Vitamin C (amperometric det.).
How can one speed-up the titrant addition (incremental vs. dynamic)?
Incremental titrant addition (INC)
The titrant is added in constant volume increments dV. Incremental titrant addition is used in non-aqueous
titrations, which sometimes have an unstable signal, and also in redox and in photometric titrations, where
the potential jump at the equivalence point occurs suddenly. Notice that in the steepest region of the curve
there are relatively few measured points.
Dynamic titrant addition (DYN)
A constant pH- or potential change per increment allows the variation of the volume increment between
minimum and maximum volume increment.
Thus, the analysis can be speeded up by using big increments in the flat regions of the titration curve. In
addition, more measured points are obtained in the steepest region of the curve leading to a more accurate
evaluation.
The second possibility is a calculation problem with the defined value for z, the equivalent number or
valency. Here one should make sure that you are in fact titrating to the correct equivalence point. An
example is the titration of sodium carbonate with HCl. If this titration is terminated after the first equivalence
point then the equivalent number that should be used for the carbonate is 1 rather than the 2 expected when
writing out the chemical reaction. The reason for this is that the reaction is a two step reaction, with the
carbonate first reacting to bicarbonate (hydrogen carbonate) and only then continuing to carbon dioxide,
sodium chloride and water. If the titration were continued until the gas bubbles are visible (carbon dioxide
formation) then z would indeed be 2.
Why do I get no result or a result of zero when, from the curve, there is a clear jump visible?
There are a few reasons for this although the most common is that too high a threshold value has been set
in the method. Print out a table of measured values and check the largest value for the first derivative. The
threshold value in the method has to be set lower than this. Generally it is suggested that the threshold be
set at approximately 50% of the maximum in the first derivative for steep curves and up to 80% for flatter
curves. Remember that the main purpose of the threshold value is to eliminate noise or false equivalence
points. Other reasons for no result include specifying the incorrect tendency (direction of the titration curve)
and a poor choice of equivalence point range.
What electrode should I use for non-aqueous titrations?
Generally there are three main electrode problems when performing a non-aqueous titration. The first is the
problem of having an aqueous electrolyte with a non-aqueous solvent. Replacing the electrolyte in the
electrode easily solves this. The second problem relates to the fact that the sample is non-conductive,
resulting in a poor electrical circuit between measuring and reference half-cells or parts of the electrode if
combined. This results in a noisy signal, particularly when using a sensor with a standard ceramic junction in
the reference. A partial solution to this problem is to use a sensor with a sleeved junction, such as the
DG113 electrode. This sensor has LiCl in ethanol as the standard electrolyte and, rather than a ceramic
junction, has a polymer sleeve resulting in a larger contact area between working and reference parts and
therefore lower noise.
The third problem is not a problem of the electrode itself, but rather the handling of the sensor. In order for a
glass (pH) sensor to function correctly, it is necessary that the glass membrane (bulb of electrode) be
hydrated. This is achieved by conditioning the electrode in deionized water. During the non-aqueous titration
this membrane is gradually dehydrated reducing the response of the electrode. To prevent this or rectify this
problem the electrode should be regularly reconditioned by soaking in water.
Why, when I perform an equivalence point titration using an automatic titrator, do I get a different
result as to when I titrate manually using a color indicator?
This discrepancy in results is primarily noticeable when performing acid/base titrations using one of the pH
indicators. The first reason for this is that these pH indicators change color over a pH range rather than at a
fixed value. The actual point at which the color change occurs is very much sample dependant and may not
coincide with the chemical equivalence point. This can result in a small discrepancy in result which is easily
nullified by standardizing the titrant using a similar method as is used for samples.
The second reason for this difference is primarily one of the sensitivity of the human eye to color change.
While a color change may have already started to occur, the human eye has still not detected any change.
This can be demonstrated by using a photometric sensor such as the METTLER TOLEDO DP5 phototrodes.
Using one of these sensors there is a clear change in light transmittance long before the human eye detects
any color change. In the typical acid/base titration using potentiometric indication with a pH sensor, the
sharp change in signal occurs at the first trace of excess acid (or base) and is therefore a more true
indication of the end point.
Why, when I titrate with sodium hydroxide (NaOH), do I sometimes see two equivalence points?
Sodium hydroxide (and potassium hydroxide) has a tendency to absorb carbon dioxide forming sodium
carbonate, which also then reacts with any acid in the sample. This results in this double inflection point
effect. Even freshly prepared sodium hydroxide solutions often show this effect. The reason for this is that
the solid sodium hydroxide (often pellets) also absorbs carbon dioxide, forming a thin layer of carbonate on
the surface. The only way to prepare fresh carbonate free sodium hydroxide solutions is to prewash the
pellets or use fresh pellets and to use freshly boiled deionized (or distilled) water. Once such a solution has
been prepared it should be protected from carbon dioxide by fitting an absorption tube filled with sodium
hydroxide on a carrier. Whenever this double inflection point is apparent when titrating with sodium
hydroxide (or potassium hydroxide) it is recommended that the solution be discarded and fresh titrant
prepared. An alternative to discarding is to boil, allow to cool and filter through a very fine mesh filter paper.