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Acid-base titration is a representative quantitative experiment commonly performed in introductory chemistry and analytical chemistry laboratories at universities.
By using a standard acid or base solution of known concentration, the concentration of an unknown sample can be determined.
In an acid-base titration report, it is important to discuss not only the titration volume and concentration calculation, but also the difference between the neutralization point and the endpoint, the transition range of the indicator, variation in titration volumes, and sources of error in endpoint determination.
This article clearly explains how to interpret acid-base titration results, how to write the discussion, sources of error, and points for improvement.
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Note:
This article is a reference intended to assist with discussions of results obtained in chemistry experiments at universities and similar institutions.
For actual experimental procedures and safety precautions, always follow the instructions in your university’s laboratory manual and those given by your instructor or TA.
- What Is Acid-Base Titration?
- Results to Examine in Acid-Base Titration
- Reference Experimental Values and Analysis Examples for the Neutralization Point and Concentration Calculation in Acid-Base Titration
- Reference Experimental Conditions
- Basics of the Neutralization Reaction
- Example of Titrating a Strong Acid With a Strong Base
- Example of Calculating the Unknown HCl Concentration
- Example of Titrating a Weak Acid With a Strong Base
- Example of Determining the Acetic Acid Concentration in Vinegar
- Example of Standardizing NaOH Standard Solution
- Example of Correction Using the Standardized Concentration
- Examples of Indicator Selection
- Example of Endpoint Determination Using Phenolphthalein
- Examples Comparing Titration Curves
- Example of Blank-Test Correction
- Effect of Over-Titration on Concentration Calculation
- Effect of CO2 Absorption by the NaOH Standard Solution
- Main Sources of Error
- Example of How to Write the Results
- Points to Connect to the Discussion
- Example Discussion Text
- Summary
- Difference Between the Neutralization Point and the Endpoint
- Indicator Transition Range and Error
- Discussion When Using Phenolphthalein
- Discussion of Variation in Titration Volumes
- Discussion When the Endpoint Is Exceeded
- Burette-Reading Error
- Error Due to Air Bubbles in the Burette Tip
- Error in Sample Volume Collected With a Volumetric Pipette
- Error Due to Standard-Solution Concentration
- Error Due to Insufficient Stirring
- What Can Be Discussed From the Titration Curve
- Concept of Concentration Calculation
- How to Write About Excluding Titration Values
- When the Result Can Be Considered Good
- Example Discussion When the Experiment Did Not Go Well
- How to Write Points for Improvement
- Difference Between a Superficial Discussion and a Good Discussion
- Examples of Expressions That Can Be Used in Reports
- Points to Check When Discussing Acid-Base Titration
- Summary
What Is Acid-Base Titration?
Acid-base titration is an analytical method that uses the neutralization reaction between an acid and a base to determine the concentration of an acid or base in a solution.
For example, an aqueous sodium hydroxide solution of known concentration can be used to determine the concentration of an aqueous acetic acid solution.
In titration, a standard solution of known concentration is gradually added from a burette, and the point at which the reaction has just been completed is determined.
The amount or concentration of the unknown sample is then calculated from the volume of standard solution used at that point.
Although the calculations in acid-base titration may appear relatively simple, in an actual report it is important to discuss matters such as “how the endpoint was determined,” “why the titration volumes varied,” and “whether the indicator was appropriate.”
Results to Examine in Acid-Base Titration
In the results of acid-base titration, organize the volume of standard solution used for titration, titration volumes from repeated measurements, the average titration volume, the calculated sample concentration, and the color change at the endpoint.
Main Items to Include in the Results
- Volume of the sample solution
- Concentration of the standard solution
- Titration volume for each trial
- Average titration volume
- Calculated sample concentration
- Type of indicator
- Color change at the endpoint
- Variation in titration values
- If any measured value was excluded, the reason for exclusion
Example of How to Write the Results:
A 10.00 mL aqueous acetic acid solution was titrated using 0.100 mol/L aqueous sodium hydroxide solution.
Phenolphthalein was used as the indicator, and the endpoint was taken as the point at which the solution changed from colorless to pale red and the color persisted for approximately 30 seconds.
The titration volumes were 8.95 mL for the first trial, 8.72 mL for the second trial, and 8.70 mL for the third trial.
Because the first trial may have exceeded the endpoint, the average of the second and third trials, 8.71 mL, was used to determine the concentration.
Reference Experimental Values and Analysis Examples for the Neutralization Point and Concentration Calculation in Acid-Base Titration
Here, reference experimental values are organized for discussing titration volume, unknown sample concentration, neutralization point, titration curve, and indicator color changes obtained in acid-base titration.
Strong acid-strong base titration, weak acid-strong base titration, standardization of standard solutions, dilution factors, blank tests, and endpoint errors are summarized in a form that is easy to use in reports.
In acid-base titration, a standard solution of known concentration is used to neutralize an acid or base of unknown concentration, and the unknown concentration is determined from the volume required for the reaction.
At the equivalence point, the amount of H+ supplied by the acid and the amount of OH− supplied by the base become exactly equivalent according to the reaction ratio.
Reference Experimental Conditions
| Item | Details |
|---|---|
| Type of titration | Neutralization titration, acid-base titration |
| Examples of standard solutions | NaOH standard solution, HCl standard solution, oxalic acid standard solution, etc. |
| Examples of unknown samples | Hydrochloric acid, acetic acid, vinegar, aqueous sodium hydrogen carbonate solution, aqueous sodium hydroxide solution, etc. |
| Measured values | Sample amount, standard-solution concentration, titration volume, endpoint, pH, dilution factor |
| Examples of indicators | Phenolphthalein, methyl orange, bromothymol blue |
| Main sources of error | Standard-solution concentration, endpoint determination, burette reading, CO2 in air, sample volume, indicator selection |
Basics of the Neutralization Reaction
The neutralization reaction between hydrochloric acid, a strong acid, and sodium hydroxide, a strong base, can be expressed as follows.
HCl + NaOH → NaCl + H2O
In this case, HCl and NaOH react in a 1:1 ratio.
Therefore, at the equivalence point, the amount of HCl is equal to the amount of NaOH.
| Type of Reaction | Example Reaction Equation | Reaction Ratio | Point to Note in Calculation |
|---|---|---|---|
| Monoprotic acid and monobasic base | HCl + NaOH → NaCl + H2O | 1 : 1 | The amounts of substance are equal |
| Diprotic acid and monobasic base | H2SO4 + 2NaOH → Na2SO4 + 2H2O | 1 : 2 | Twice as much base as acid is required |
| Monoprotic acid and dibasic base | 2HCl + Ca(OH)2 → CaCl2 + 2H2O | 2 : 1 | Twice as much acid as base is required |
| Weak acid and strong base | CH3COOH + NaOH → CH3COONa + H2O | 1 : 1 | The pH at the equivalence point is greater than 7 |
Example of Titrating a Strong Acid With a Strong Base
The following are reference data obtained by titrating 25.00 mL of HCl of unknown concentration with 0.1000 mol/L NaOH standard solution.
| Trial | Sample Volume | NaOH Concentration | NaOH Titration Volume | Endpoint Assessment |
|---|---|---|---|---|
| 1st | 25.00 mL | 0.1000 mol/L | 18.72 mL | Slightly dark red |
| 2nd | 25.00 mL | 0.1000 mol/L | 18.64 mL | Good |
| 3rd | 25.00 mL | 0.1000 mol/L | 18.62 mL | Good |
| 4th | 25.00 mL | 0.1000 mol/L | 18.65 mL | Good |
| Average | 25.00 mL | 0.1000 mol/L | 18.64 mL | Average of the 2nd to 4th trials |
This is an example in which the first trial is judged to have been slightly over-titrated while confirming the endpoint color, and the average of the second to fourth trials, 18.64 mL, is used as the representative value.
Example of Calculating the Unknown HCl Concentration
HCl and NaOH react in a 1:1 ratio.
When the NaOH concentration is 0.1000 mol/L and the average titration volume is 18.64 mL,
n(NaOH) = 0.1000 mol/L × 0.01864 L = 1.864×10−3 mol
From the 1:1 reaction ratio,
n(HCl) = 1.864×10−3 mol
The concentration in 25.00 mL of the HCl sample is,
C(HCl) = 1.864×10−3 mol ÷ 0.02500 L = 0.07456 mol/L
Therefore, the concentration of the unknown aqueous HCl solution is determined to be 0.07456 mol/L.
Example of Titrating a Weak Acid With a Strong Base
The following are reference data obtained by titrating 25.00 mL of aqueous acetic acid solution with 0.1000 mol/L NaOH standard solution.
| NaOH Added | pH | Titration Stage | Direction of Discussion |
|---|---|---|---|
| 0.00 mL | 2.88 | Before titration | Because it is a weak acid, the pH is higher than that of a strong acid |
| 5.00 mL | 4.14 | Buffer region | Acetic acid and acetate ions coexist |
| 12.50 mL | 4.76 | Half-neutralization point | pH ≒ pKa |
| 20.00 mL | 5.36 | Before the equivalence point | Gradual increase |
| 24.50 mL | 6.75 | Immediately before the equivalence point | The change becomes large |
| 25.00 mL | 8.72 | Equivalence point | Basic due to hydrolysis of acetate ions |
| 25.50 mL | 10.70 | After the equivalence point | NaOH is in excess |
| 30.00 mL | 11.80 | After the equivalence point | The effect of the strong base is large |
In titration of a weak acid with a strong base, the pH at the equivalence point is greater than 7.
This is because acetate ions formed at the equivalence point act as the conjugate base of the weak acid and undergo partial hydrolysis with water.
Example of Determining the Acetic Acid Concentration in Vinegar
Suppose vinegar is diluted 10-fold and 10.00 mL of the diluted solution is titrated with 0.1000 mol/L NaOH.
The following is an example calculation when the average titration volume is 8.35 mL.
| Item | Value | Calculation / Meaning |
|---|---|---|
| Dilution factor | 10-fold | The original vinegar was diluted 10-fold |
| Volume of diluted solution collected | 10.00 mL | Used for titration |
| NaOH concentration | 0.1000 mol/L | Standard solution |
| NaOH titration volume | 8.35 mL | Average value |
| Amount of acetic acid in the diluted solution | 8.35×10−4 mol | 0.1000 × 0.00835 |
| Acetic acid concentration in the diluted solution | 0.0835 mol/L | 8.35×10−4 ÷ 0.01000 |
| Acetic acid concentration in the original vinegar | 0.835 mol/L | 0.0835 × 10 |
Using 60.05 g/mol as the molar mass of acetic acid, the amount of acetic acid in the original vinegar is calculated as follows.
0.835 mol/L × 60.05 g/mol = 50.1 g/L
This corresponds to approximately 5.01 g per 100 mL, so it can be expressed as approximately 5.0% as an approximate mass-volume percentage.
Example of Standardizing NaOH Standard Solution
Aqueous NaOH solution readily absorbs CO2 from the air, so its exact concentration may change.
Therefore, it may be standardized using a standard substance such as oxalic acid.
H2C2O4 + 2NaOH → Na2C2O4 + 2H2O
| Item | Value | Calculation / Meaning |
|---|---|---|
| Oxalic acid standard-solution concentration | 0.05000 mol/L | Known concentration |
| Volume of oxalic acid collected | 25.00 mL | 0.02500 L |
| Amount of oxalic acid | 1.250×10−3 mol | 0.05000 × 0.02500 |
| Required amount of NaOH | 2.500×10−3 mol | Twice the amount of oxalic acid |
| NaOH titration volume | 25.30 mL | Average value in standardization |
| Actual NaOH concentration | 0.09881 mol/L | 2.500×10−3 ÷ 0.02530 |
Using the concentration of 0.09881 mol/L determined by standardization rather than the labeled concentration of 0.1000 mol/L allows the unknown sample concentration to be determined more accurately.
Example of Correction Using the Standardized Concentration
| Calculation Condition | NaOH Concentration | HCl Titration Volume | Calculated HCl Concentration | Trend in the Result |
|---|---|---|---|---|
| Using the labeled concentration | 0.1000 mol/L | 18.64 mL | 0.07456 mol/L | Slight overestimation |
| Using the standardized concentration | 0.09881 mol/L | 18.64 mL | 0.07367 mol/L | After correction |
If the actual concentration of the NaOH standard solution is lower than the labeled value, calculating with the labeled concentration overestimates the acid concentration.
Examples of Indicator Selection
| Titration Combination | pH Near the Equivalence Point | Examples of Suitable Indicators | Direction of Discussion |
|---|---|---|---|
| Strong acid + strong base | Approximately 7 | BTB, phenolphthalein, etc. | The sharp-change range is broad and indicators are relatively easy to select |
| Weak acid + strong base | Greater than 7 | Phenolphthalein | An indicator that changes color on the basic side is suitable |
| Strong acid + weak base | Less than 7 | Methyl orange, etc. | An indicator that changes color on the acidic side is suitable |
| Weak acid + weak base | Small sharp change | May be unclear with an indicator method | Potentiometric titration is effective |
If the transition range of the indicator does not fall within the sharp pH-change range near the equivalence point, the endpoint and equivalence point are more likely to differ.
Example of Endpoint Determination Using Phenolphthalein
| Titration Stage | State of the Solution | Example Color | Assessment |
|---|---|---|---|
| Before titration | Excess acid | Colorless | Before the endpoint |
| Before the equivalence point | Acid still remains | Colorless | Continue titration |
| Near the endpoint | NaOH is slightly in excess | Very pale red | Endpoint |
| Over-titration | NaOH is greatly in excess | Dark red | Titration volume is too large |
With phenolphthalein, the endpoint is taken not at a dark red color but at the point where a very pale red color remains for a certain period of time.
Attempting to make the color darker causes over-titration and overestimation of the acid concentration.
Examples Comparing Titration Curves
| Type of Titration | Initial pH | pH at the Equivalence Point | Feature of pH Change | Direction of Discussion |
|---|---|---|---|---|
| Strong acid titrated with strong base | Low | Approximately 7 | Sharp increase near the equivalence point | Approaches neutrality through neutralization |
| Weak acid titrated with strong base | Higher than a strong acid | Greater than 7 | Has a buffer region | Hydrolysis of the conjugate base |
| Strong acid titrated with weak base | Low | Less than 7 | Equivalence point on the acidic side | Effect of the conjugate acid |
| Weak acid titrated with weak base | Intermediate | Depends on conditions | Small sharp pH change | Indicator selection is difficult |
Example of Blank-Test Correction
If reagents or water contain components that consume acid or base, correction may be performed using a blank test.
| Measurement | NaOH Titration Volume | Concept of Correction |
|---|---|---|
| Sample titration | 18.64 mL | Consumption from sample + reagents |
| Blank test | 0.06 mL | Consumption from water, reagents, and indicator |
| Corrected titration volume | 18.58 mL | 18.64 − 0.06 |
Even if the blank-test correction volume is small, its relative effect may become large for low-concentration samples.
Effect of Over-Titration on Concentration Calculation
| Condition | NaOH Titration Volume | Calculated HCl Concentration | Trend in the Result |
|---|---|---|---|
| Appropriate endpoint | 18.64 mL | 0.07456 mol/L | Reference |
| 0.05 mL over-titration | 18.69 mL | 0.07476 mol/L | Slightly high |
| 0.10 mL over-titration | 18.74 mL | 0.07496 mol/L | High |
| 0.20 mL over-titration | 18.84 mL | 0.07536 mol/L | Clearly overestimated |
If too much standard solution is added beyond the endpoint, the amount of acid or base contained in the unknown sample is estimated to be greater than it actually is.
Effect of CO2 Absorption by the NaOH Standard Solution
Aqueous NaOH solution may absorb CO2 from the air and form carbonate.
This changes the effective concentration of NaOH and affects the titration result.
| Condition of NaOH | Actual Effective Concentration | When Calculated Using the Labeled Concentration | Direction of Discussion |
|---|---|---|---|
| Immediately after preparation | 0.1000 mol/L | Little problem | Reference |
| Left for a short period | 0.0988 mol/L | Acid concentration is overestimated | Standardization is required |
| Left for a long period | 0.0965 mol/L | Large error | Re-standardization or re-preparation is required |
When NaOH is used as a standard solution, it is important to confirm its actual concentration by standardization.
Main Sources of Error
| Source of Error | Effect on the Measured Value | Trend in the Result | Improvement / Check |
|---|---|---|---|
| Over-titration of the endpoint | Titration volume becomes larger | Unknown concentration is overestimated | Use the point where a pale color remains as the endpoint |
| Deviation in standard-solution concentration | Affects the entire calculation | Overestimation or underestimation | Use the standardized value |
| Burette-reading error | Volume shifts | Directly affects concentration calculation | Read with the line of sight aligned |
| Pipetting error | Sample amount shifts | Affects concentration calculation | Use the correct collection volume |
| Inappropriate indicator selection | Endpoint and equivalence point differ | Systematic error occurs | Use an indicator suitable for the pH at the equivalence point |
| CO2 absorption by NaOH | Effective concentration decreases | Error occurs if the labeled concentration is used | Store tightly sealed and standardize |
| No blank-test correction | Includes consumption derived from reagents | May overestimate the concentration | Perform a blank test |
Example of How to Write the Results
A 25.00 mL aqueous HCl solution of unknown concentration was titrated with 0.1000 mol/L NaOH standard solution.
The average of three satisfactory titration volumes was 18.64 mL.
Because HCl and NaOH react in a 1:1 ratio, the amount of NaOH is equal to the amount of HCl.
The calculation gave an HCl concentration of 0.07456 mol/L.
When phenolphthalein was used as the indicator, the endpoint was taken as the point at which a very pale red color remained for a while.
If titration is continued until a dark red color appears, NaOH is added in excess and the HCl concentration is estimated higher than the actual value.
Therefore, judgment of the endpoint color greatly affects the titration result.
The aqueous NaOH solution used as the standard solution readily absorbs CO2 from the air, so its effective concentration may change.
If standardization gives an actual concentration of 0.09881 mol/L, recalculation using this value gives an HCl concentration of 0.07367 mol/L.
This difference shows that standardization of the standard solution is important for the accuracy of concentration calculations.
Points to Connect to the Discussion
In the discussion of acid-base titration, it is important not only to calculate the concentration from the titration volume, but also to explain the reaction ratio, indicator, difference between the equivalence point and endpoint, standardization of the standard solution, dilution factor, and sources of error in relation to one another.
- Can you correctly calculate the concentration using the reaction ratio between the acid and base?
- Can you determine the amount of substance from the concentration and titration volume of the standard solution?
- Can you determine the concentration by dividing by the amount of unknown sample?
- If vinegar or another sample was diluted, can you determine the original sample concentration by multiplying by the dilution factor?
- Can you explain that the pH at the equivalence point differs between strong acid-strong base titration and weak acid-strong base titration?
- Can you explain that the pH is close to pKa at the half-neutralization point?
- Can you discuss whether the transition range of the indicator is appropriate for the equivalence-point region?
- Can you explain why standardization of the standard solution is necessary?
- Can you discuss over-titration of the endpoint, CO2 absorption, burette reading, and blank testing as sources of error?
Example Discussion Text
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In this experiment, the concentration of an unknown aqueous HCl solution was determined by acid-base titration.
Because HCl and NaOH undergo a neutralization reaction in a 1:1 ratio, the amount of HCl is equal to the amount of NaOH at the equivalence point.
From the average titration volume of 18.64 mL and the NaOH concentration of 0.1000 mol/L, the amount of NaOH was 1.864×10−3 mol, and the HCl concentration was determined to be 0.07456 mol/L.
The endpoint was judged as the point at which a pale red color of phenolphthalein remained.
Because phenolphthalein shows a red color on the basic side, the color remains at the point where NaOH becomes slightly excessive.
Therefore, the endpoint does not necessarily completely coincide with the exact equivalence point.
Attempting to confirm a darker color causes over-titration and becomes a source of overestimation of the unknown acid concentration.
When acetic acid, a weak acid, is titrated with a strong base, the pH at the equivalence point is greater than 7.
This is because acetate ions formed at the equivalence point react with water and make the solution basic.
In addition, at the half-neutralization point, the concentrations of acetic acid and acetate ions are equal, so the pH is close to the pKa.
In this way, the shape of the titration curve and the pH at the equivalence point change depending on the strength of the acid.
The aqueous NaOH solution used as the standard solution may absorb CO2 from the air and change in concentration.
If the actual concentration is lower than the labeled value, calculating with the labeled concentration overestimates the unknown acid concentration.
Therefore, for accurate quantitative analysis, it is necessary to standardize NaOH using oxalic acid or another substance and perform calculations using the actual concentration.
Possible sources of error include individual differences in endpoint determination, deviations in standard-solution concentration, burette and pipette reading errors, inappropriate indicator selection, and failure to correct for a blank test.
In particular, because the titration volume is directly related to the concentration calculation, it is important to add the standard solution in small amounts near the endpoint and determine the endpoint using the same color tone as the criterion.
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Summary
In acid-base titration, the concentration of an unknown sample is determined from the titration volume of the standard solution based on the reaction ratio between the acid and base.
The equivalence point is the point at which the reaction is stoichiometrically just complete, while the endpoint is the observed end of titration determined using an indicator or other method.
This reference example covered strong acid-strong base titration, weak acid-strong base titration, acetic acid concentration in vinegar, standardization of NaOH standard solution, indicator selection, titration curves, blank-test correction, over-titration, CO2 absorption, and sources of error.
In a report, it is useful to discuss not only the calculation results, but also the difference between the equivalence point and endpoint, the suitability of the indicator, and the reliability of the standard solution.
Difference Between the Neutralization Point and the Endpoint
An important point in the discussion of acid-base titration is the difference between the “neutralization point” and the “endpoint.”
The neutralization point is the point at which the acid and base have reacted in exactly the stoichiometric ratio.
The endpoint, on the other hand, is the point at which the experimenter stops the titration based on an indicator color change or similar observation.
| Item | Meaning | Characteristic |
|---|---|---|
| Neutralization point | The theoretical point at which the acid and base have reacted exactly | Determined stoichiometrically |
| Endpoint | The point at which titration is stopped based on an indicator color change or similar observation | Determined by observation |
Ideally, the neutralization point and endpoint should coincide, but in practice they may not completely coincide because of the transition range of the indicator and visual judgment.
This difference causes titration error.
Example Discussion:
In acid-base titration, the neutralization point and endpoint do not necessarily coincide completely.
The neutralization point is the point at which the acid and base have reacted in stoichiometrically equivalent amounts, whereas the endpoint is the point determined by the experimenter from the color change of the indicator.
Therefore, differences in the indicator transition range or in color judgment may cause the endpoint to shift slightly from the neutralization point and produce an error in the titration volume.
Indicator Transition Range and Error
In acid-base titration, an indicator may be used to determine the endpoint.
An indicator changes color over a certain pH range.
Therefore, the indicator used for the titration must change color near the neutralization point.
For example, in titration of a strong acid with a strong base, the pH changes sharply near the neutralization point, so a relatively wide range of indicators can be used.
On the other hand, in titration of a weak acid with a strong base or a strong acid with a weak base, the pH at the neutralization point shifts away from 7, so indicator selection becomes important.
| Titration Combination | Feature Near the Neutralization Point | Discussion Point |
|---|---|---|
| Strong acid and strong base | pH changes sharply near the neutralization point | Endpoint determination is relatively easy |
| Weak acid and strong base | Neutralization point is on the basic side | An indicator that changes color on the basic side is suitable |
| Strong acid and weak base | Neutralization point is on the acidic side | An indicator that changes color on the acidic side is suitable |
| Weak acid and weak base | pH change is small | The endpoint is difficult to determine with an indicator |
Example Discussion:
If the transition range of the indicator does not completely correspond to the pH change near the neutralization point, the endpoint may shift from the neutralization point.
In particular, in titration of a weak acid with a strong base, the neutralization point is on the basic side, so if the transition range of the indicator used is inappropriate, an error may occur in the titration volume.
Therefore, the choice of indicator is considered to affect the accuracy of the titration result.
Discussion When Using Phenolphthalein
Phenolphthalein is an indicator that is colorless under acidic to near-neutral conditions and shows a red or pale red color on the basic side.
It is often used in titrations such as those between a weak acid and a strong base.
At the endpoint, a pale red color that remains for a while, rather than a dark red color, is often used as a guide.
If titration is continued until the solution becomes dark red, the endpoint may have been exceeded.
Example Discussion:
In titration using phenolphthalein, the point at which a pale red color persists for a certain period of time is judged to be the endpoint.
However, because the color change is judged visually, individual differences may occur in how intense the pale red color must be before it is judged to be the endpoint.
If titration is continued beyond the endpoint until the solution becomes dark red, the titration volume becomes larger than the actual value and the calculated sample concentration may be overestimated.
Discussion of Variation in Titration Volumes
In titration experiments, repeated measurements may not produce exactly the same titration volume.
Possible causes of variation include differences in endpoint determination, burette-reading errors, deviations in the amount of sample collected, insufficient stirring, and differences in dropwise addition rate.
| Cause | What Happens | Effect on the Result |
|---|---|---|
| Differences in endpoint determination | The timing used to judge the color change differs | Titration volumes vary |
| Burette-reading error | The initial or endpoint value is misread | Error occurs in titration volume |
| Deviation in sample volume | The amount of substance in the sample changes | The required titration volume changes |
| Insufficient stirring | pH changes locally | Endpoint determination becomes unstable |
| Dropwise addition is too fast | The endpoint is easily exceeded | Titration volume becomes larger |
Example Discussion:
One possible cause of variation in the titration volumes is differences in endpoint determination.
Because the color change of the indicator is judged visually, the titration volume changes depending on the point at which the pale red color is judged to have persisted sufficiently to represent the endpoint.
In addition, if the addition rate near the endpoint is too fast, excess standard solution may be added beyond the required amount, causing the titration volume to become larger.
Discussion When the Endpoint Is Exceeded
A common source of error in acid-base titration is adding too much standard solution beyond the endpoint.
If the endpoint is exceeded, the recorded titration volume becomes larger than the amount actually required.
As a result, the concentration calculation is also affected.
For example, when determining the concentration of an acid by titrating it with a base, if the titration volume is read as too large, the amount of acid is estimated to be greater than it actually is.
Therefore, the calculated acid concentration may become higher than the actual value.
Example Discussion:
If standard solution is added beyond the endpoint, the recorded titration volume becomes larger than the amount actually required for neutralization.
Therefore, the amount of acid or base contained in the sample is overestimated, and the calculated concentration may become higher than the actual value.
Because pH changes rapidly near the endpoint, the addition rate should be reduced and the operation should be performed while confirming the pale color change.
Burette-Reading Error
With a burette, the initial value before titration and the endpoint value after titration are read, and the titration volume is determined from the difference.
If either reading contains an error, an error also occurs in the titration volume.
If the line of sight is not at the same height as the scale when reading the meniscus, parallax may cause the volume to be read as larger or smaller than the actual value.
Example Discussion:
Parallax when reading the burette scale is also considered a source of error in the titration volume.
If the line of sight is not at the same height as the meniscus, the initial or endpoint value may be read as larger or smaller than the actual value.
Because the titration volume is determined from the difference between the initial and endpoint values, reading errors are considered to directly affect the concentration calculation.
Error Due to Air Bubbles in the Burette Tip
If an air bubble remains in the tip of the burette, the liquid level appears to decrease when the bubble is expelled during titration.
However, that volume of liquid has not actually been added to the sample solution, so the titration volume may be overestimated.
Example Discussion:
If an air bubble remained in the burette tip, the liquid level on the burette scale would fall when the bubble was expelled during titration.
However, the corresponding volume of standard solution would not actually have been added to the sample solution, so the titration volume may have been overestimated.
As a result, an error may have occurred in the calculated sample concentration.
Error in Sample Volume Collected With a Volumetric Pipette
In acid-base titration, a fixed volume of sample solution may be collected using a volumetric pipette.
If the liquid level is not aligned correctly with the calibration mark, if air bubbles are present, or if rinsing with the solution is insufficient, the collected sample volume may deviate from the specified amount.
Example Discussion:
When collecting the sample solution with a volumetric pipette, if the liquid level was not aligned accurately with the calibration mark, the collected sample volume would deviate from the specified amount.
If the collected amount was too large, more standard solution would also be required for neutralization, whereas if the collected amount was too small, the titration volume would also become smaller.
Therefore, error in the sample volume collected with a volumetric pipette is considered to affect the calculated concentration.
Error Due to Standard-Solution Concentration
Titration assumes that the concentration of the standard solution is accurate.
If the actual concentration of the standard solution differs from the labeled or calculated value, the determined concentration of the unknown sample also shifts.
For example, aqueous sodium hydroxide solution may absorb carbon dioxide from the air, causing its concentration to change.
Errors in weighing and volumetric-flask operation during preparation of the standard solution may also have an effect.
Example Discussion:
One possible reason the calculated sample concentration differed from the theoretical value is that the concentration of the standard solution was not accurate.
If the actual concentration of the standard solution was lower than expected, a larger titration volume would be required to neutralize the same amount of substance.
In addition, aqueous sodium hydroxide solution may absorb carbon dioxide from the air, so its concentration may have changed depending on storage conditions.
Error Due to Insufficient Stirring
During titration, the added standard solution must mix uniformly throughout the sample solution.
If stirring is insufficient, the pH may change locally and the color of the indicator may change temporarily.
As a result, the endpoint may be judged too early, or conversely, too much additional titrant may be added.
Example Discussion:
If stirring during titration was insufficient, the added standard solution may not have mixed uniformly throughout the sample solution and the pH may have changed locally.
As a result, the indicator color may have changed temporarily and caused incorrect endpoint determination.
Such insufficient mixing is considered to cause variation in titration volumes and errors in concentration calculations.
What Can Be Discussed From the Titration Curve
If the pH during titration is measured using a pH meter or similar device, a titration curve can be created.
The titration curve shows the change in pH with respect to the volume of standard solution added.
Because pH changes greatly near the neutralization point, the equivalence point and suitability of the indicator can be discussed more easily.
| Feature of the Titration Curve | What Can Be Discussed |
|---|---|
| There is a region where pH changes sharply | Neutralization is considered to have progressed near the equivalence point |
| The sharp-change range is wide | The endpoint is easy to determine with an indicator |
| The sharp-change range is small | Endpoint determination is difficult and error is likely to be larger |
| The pH at the equivalence point differs from 7 | The effect of a weak acid or weak base is considered |
Example Discussion:
On the titration curve, the pH changed sharply near a certain titration volume.
This sharp pH change indicates that the acid and base had reacted in nearly equivalent amounts, and this region is considered to correspond to the neutralization point.
If the transition range of the indicator falls within this sharp pH-change region, visual endpoint determination is considered to have been relatively appropriate.
Concept of Concentration Calculation
In acid-base titration, concentration is determined using the quantitative relationship of the neutralization reaction.
If the acid and base react in a 1:1 ratio, the point where the amounts of acid and base are equal is used.
However, if the valences of the acid or base differ, the coefficients of the reaction equation must be taken into account.
Amount of substance mol = concentration mol/L × volume L
In calculations, it is important to convert mL to L, use consistent significant figures, and select appropriate values when using an average titration volume.
Example Discussion of the Calculation Result:
The average of the second and third titration volumes, for which endpoint determination was appropriate, was used in the concentration calculation.
In the first trial, the solution showed a dark red color because the endpoint was exceeded, so the titration volume was likely to be too large.
Including such a value in the average would also overestimate the calculated concentration, so excluding it from the calculation is considered appropriate.
How to Write About Excluding Titration Values
In titration, a value that clearly exceeded the endpoint or differed greatly from the other measurements may be excluded when calculating the average.
However, when excluding a value, the reason for exclusion must be explained in the report.
It is important to base the reason on observed facts so that it does not appear that the value was excluded simply because it was inconvenient.
Examples include “the solution became dark red,” “the endpoint was clearly exceeded,” or “the value differed greatly from the other titration values.”
Example Discussion:
The titration volume in the first trial was larger than the other measured values, and the solution showed a dark red color at the endpoint.
This is considered to have occurred because excess standard solution was added beyond the endpoint.
Therefore, the first value was excluded from the calculation of the average titration volume, and the second and third values, for which endpoint determination was appropriate, were used.
When the Result Can Be Considered Good
A good result in acid-base titration is indicated when multiple titration volumes agree closely, the color change at the endpoint is appropriate, and the determined concentration is close to the theoretical or labeled value.
If a titration curve is created, it is also important that a clear sharp pH-change region can be observed.
Example Discussion:
The titration volumes from multiple trials showed similar values, and no large variation was observed.
This suggests that the reproducibility of endpoint determination was relatively high.
In addition, because the calculated sample concentration was close to the expected value, the concentration of the standard solution, sample volume, and titration procedure are considered to have been generally appropriate.
Example Discussion When the Experiment Did Not Go Well
If titration values varied, differed greatly from the theoretical value, or the endpoint color was difficult to determine, consider where the cause may have been among endpoint determination, the standard solution, apparatus, and procedure.
Example Discussion:
One possible reason large variation was observed in the titration volumes is unstable endpoint determination.
Because the indicator color change is judged visually, the titration volume changes depending on the point at which the pale color change is judged to represent the endpoint.
In addition, if the addition rate near the endpoint was too fast, excess standard solution may have been added, causing the titration volume to become larger.
These factors are considered to have produced errors in the calculated sample concentration.
How to Write Points for Improvement
In the discussion of acid-base titration, including points for improvement as well as sources of error makes the report easier to organize.
It is important to write improvements that correspond to the actual sources of error considered.
Methods for Improving Endpoint Determination
- Add the standard solution one drop at a time near the endpoint
- Titrate while thoroughly stirring the solution
- Use the point at which a pale color change persists for a certain period of time as the endpoint
- Do not continue titration until a dark color appears
- Perform multiple titrations to confirm reproducibility
Methods for Reducing Errors Caused by Apparatus
- Read the burette scale at the same height as the meniscus
- Remove air bubbles from the burette tip before titration
- Align the volumetric-pipette calibration mark accurately
- Rinse the apparatus with the solution to be used
- Check the concentration and storage condition of the standard solution
Example of How to Write Points for Improvement:
To reduce variation in titration volumes, the standard solution should be added one drop at a time near the endpoint and the color change should be observed while thoroughly stirring the solution.
In addition, it is important to read the burette scale at the same height as the meniscus to reduce parallax error.
These measures are considered to improve the reproducibility of endpoint determination and titration volume.
Difference Between a Superficial Discussion and a Good Discussion
In a discussion of acid-base titration, simply writing that “the endpoint shifted” or “the titration volumes varied” results in a superficial discussion.
A persuasive discussion can be produced by explaining how each operation affected the titration volume and concentration calculation.
| Superficial Discussion | Good Discussion |
|---|---|
| It was difficult to determine the endpoint. | Because the indicator color change is judged visually, individual differences may occur in the point at which the pale color change is judged to represent the endpoint. If titration continues beyond the endpoint, the titration volume becomes larger than the actual value and the calculated concentration may be overestimated. |
| There was an error in the titration volume. | If parallax occurred when reading the initial or endpoint value on the burette, a reading error would occur in the titration volume. Because the titration volume is used directly in the concentration calculation, the calculated sample concentration is also considered to be affected. |
| The concentration differed from the theoretical value. | Possible reasons the calculated concentration differed from the theoretical value include deviation in endpoint determination, changes in the standard-solution concentration, and errors in the sample volume collected. In particular, if titration continued beyond the endpoint, the titration volume would become too large and the sample concentration could also be overestimated. |
Examples of Expressions That Can Be Used in Reports
The following expressions can be used when writing the results and discussion of acid-base titration.
Adjust the necessary parts according to your own experimental results.
- The neutralization point is the point at which the acid and base have reacted in stoichiometrically equivalent amounts, while the endpoint is the point determined by the color change of the indicator.
- If the transition range of the indicator and the pH at the neutralization point do not completely coincide, the endpoint may shift from the neutralization point.
- Because endpoint determination was performed visually, individual differences may have occurred in the timing used to judge the color change.
- If titration continued beyond the endpoint, the titration volume would become larger than the actual value and the calculated concentration might be overestimated.
- Parallax when reading the burette scale may have caused an error in the titration volume.
- If an air bubble remained in the burette tip, the titration volume may have been overestimated.
- If the concentration of the standard solution was not accurate, a systematic error would also occur in the calculated sample concentration.
- Because the titration volumes from multiple trials were close to one another, the reproducibility of endpoint determination is considered relatively high.
- Adding the standard solution one drop at a time near the endpoint can reduce errors caused by excess titration.
Points to Check When Discussing Acid-Base Titration
Checking the following points before writing the report makes the discussion easier to write.
- Can you explain the difference between the neutralization point and the endpoint?
- Was the indicator used appropriate?
- Was the color change at the endpoint clear?
- Did you avoid titrating beyond the endpoint?
- Was there variation in the titration volumes?
- If any measured value was excluded, did you state the reason?
- Have you considered burette-reading errors?
- Was there any air bubble in the burette tip?
- Was there any error in the sample volume collected with the volumetric pipette?
- Was the concentration of the standard solution accurate?
- Was stirring sufficient?
- Have you explained how the error affected the concentration calculation?
Summary
Acid-base titration is a basic analytical experiment that determines the concentration of an unknown sample using a neutralization reaction.
In a report, it is important to discuss not only the titration volume and concentration calculation, but also the difference between the neutralization point and endpoint, the transition range of the indicator, and sources of error in endpoint determination.
Sources of error in titration volume include titration beyond the endpoint, burette-reading errors, air bubbles in the burette tip, deviations in the amount collected with a volumetric pipette, changes in the concentration of the standard solution, and insufficient stirring.
These errors directly affect the calculated sample concentration.
In the discussion, rather than simply writing that “the titration did not go well,” specifically explain which operation made the titration volume larger or smaller and how that affected the concentration calculation.
More reliable results can be obtained by carefully adding the titrant near the endpoint and comparing multiple titration values.
