Acid and Base Concentrations
Acids and Bases
An Arrhenius acid produces hydrogen ions when it is dissolved in water:
HA + H2O → H+(aq) + A-(aq)
Here, HA is the non-dissociated aci…
An Arrhenius acid is a substance that produces hydrogen ions when it dissolves in water, while a base produces hydroxide ions. Hydrogen ions immediately react with water to form hydronium ions, but for simplicity, we'll keep thinking of them as hydrogen ions. Depending on the amount of hydrogen ions or hydroxide ions in the solution, it is considered acidic or basic.
We measure the amount of acidity or basicity using pH, which is calculated as the negative log of the concentration of hydrogen ions. So, pH values under 7 are acidic, and pH values above 7 are basic. pH 7 is neutral.
Acids and bases are also compared based on their strength, which is different from their pH. An acid's strength is related to how easily the hydrogen ion dissociates from the anion, called the conjugate base. The same idea follows for a base in reference to the hydroxide ion and its conjugate acid. We can assign a value to that strength using the acid dissociation constant, or Ka.
Ka is defined using the concentrations of the non-dissociated acid and the dissociated hydrogen ions and conjugate base. You may often see this relationship represented as pKa, which is simply the negative log of the Ka. The smaller the pKa, the stronger the acid.
Some acids, like hydrochloric acid, are monoprotic, meaning that they can dissociate only one hydrogen ion. Polyprotic acids, like phosphoric acid, can dissociate several hydrogen ions. Each dissociation has its own pKa.
So, how can we determine pKa? One way is to perform an acid-base titration. Titration is performed by slowly adding a solution of known concentration to a solution of unknown concentration while observing the reaction between them. In this case, the acid reacts with the base in a neutralization reaction to form a salt and water.
So, if we want to measure the concentration of hydrogen ions in an acid, we can simply titrate with a strong base with a known hydroxide ion concentration until the acid is neutralized. To perform a titration accurately, the base needs to be standardized — meaning that you know the exact hydroxide ion concentration. This is not always straightforward.
For example, NaOH, which you will use in your experiment, is very hygroscopic, meaning that it absorbs water from the atmosphere. This happens to NaOH both as a solid and in solution. So, the true concentration of a NaOH solution may be lower than you would expect.
To determine the exact concentration of NaOH, we must first perform an acid-base titration. To do this, you must use the base to titrate an acid with a known concentration. Potassium hydrogen phthalate, KHP, is a non-hygroscopic acid, so we can accurately calculate its concentration from its mass.
We can see when the titration is complete — meaning that the acid is neutralized — by using a pH indicator like phenolphthalein. Phenolphthalein is neutral and colorless between about pH 0 and pH 8.
As the pH increases, two hydrogen ions dissociate. This anionic form is pink. So, when we begin the titration, the KHP solution is acidic and the phenolphthalein is colorless. As we add NaOH and the hydrogen ions are neutralized, the pH increases.
In this reaction, the solution is neutral when equal amounts of acid and base have been mixed together. After that, the addition of a little more NaOH makes the pH basic and the solution turns pink. This is referred to as the endpoint. If we know the moles of KHP and the volume of NaOH used to neutralize it, we can calculate the exact concentration of the base.
Once we have a standardized base, we can determine the pKa of an acid by titrating a known concentration of the acid with our standardized base while monitoring the pH. The plot of pH versus the volume of base added is called a titration curve. The curve usually follows an S or sigmoidal shape, where the inflection point of the steepest part of the curve denotes an equivalence point.
Here, the moles of hydroxide ions and dissociated hydrogen ions are equal. Like pKa, we'll see one equivalence point for each dissociated hydrogen ion. So, a monoprotic acid has only one equivalence point, and a triprotic acid has three.
When we perform the titration, we will know that we have passed the equivalence point when the pH indicator just barely turns from colorless to pink. This is called the titration endpoint. Like when we standardize the base, this is when the solution has a small excess of hydroxide ions and thus is slightly basic.
Another inflection point in the graph occurs halfway to the equivalence point. Here, the concentrations of the dissociated and non-dissociated acids are equal. Thus, the pH at this point is equal to the pKa. So, if we perform a titration and determine the equivalence point volume, then we can calculate pKa as the pH at half of this volume.
In this lab, you'll first standardize your base and then perform a titration using that standardized base to determine two pKa’s of a polyprotic acid.
An Arrhenius acid is a substance that produces hydrogen ions when it dissolves in water, while a base produces hydroxide ions. Hydrogen ions immediately react with water to form hydronium ions, but for simplicity, we'll keep thinking of them as hydrogen ions. Depending on the amount of hydrogen ions or hydroxide ions in the solution, it is considered acidic or basic.
We measure the amount of acidity or basicity using pH, which is calculated as the negative log of the concentration of hydrogen ions. So, pH values under 7 are acidic, and pH values above 7 are basic. pH 7 is neutral.
Acids and bases are also compared based on their strength, which is different from their pH. An acid's strength is related to how easily the hydrogen ion dissociates from the anion, called the conjugate base. The same idea follows for a base in reference to the hydroxide ion and its conjugate acid. We can assign a value to that strength using the acid dissociation constant, or Ka.
Ka is defined using the concentrations of the non-dissociated acid and the dissociated hydrogen ions and conjugate base. You may often see this relationship represented as pKa, which is simply the negative log of the Ka. The smaller the pKa, the stronger the acid.
Some acids, like hydrochloric acid, are monoprotic, meaning that they can dissociate only one hydrogen ion. Polyprotic acids, like phosphoric acid, can dissociate several hydrogen ions. Each dissociation has its own pKa.
So, how can we determine pKa? One way is to perform an acid-base titration. Titration is performed by slowly adding a solution of known concentration to a solution of unknown concentration while observing the reaction between them. In this case, the acid reacts with the base in a neutralization reaction to form a salt and water.
So, if we want to measure the concentration of hydrogen ions in an acid, we can simply titrate with a strong base with a known hydroxide ion concentration until the acid is neutralized. To perform a titration accurately, the base needs to be standardized — meaning that you know the exact hydroxide ion concentration. This is not always straightforward.
For example, NaOH, which you will use in your experiment, is very hygroscopic, meaning that it absorbs water from the atmosphere. This happens to NaOH both as a solid and in solution. So, the true concentration of a NaOH solution may be lower than you would expect.
To determine the exact concentration of NaOH, we must first perform an acid-base titration. To do this, you must use the base to titrate an acid with a known concentration. Potassium hydrogen phthalate, KHP, is a non-hygroscopic acid, so we can accurately calculate its concentration from its mass.
We can see when the titration is complete — meaning that the acid is neutralized — by using a pH indicator like phenolphthalein. Phenolphthalein is neutral and colorless between about pH 0 and pH 8.
As the pH increases, two hydrogen ions dissociate. This anionic form is pink. So, when we begin the titration, the KHP solution is acidic and the phenolphthalein is colorless. As we add NaOH and the hydrogen ions are neutralized, the pH increases.
In this reaction, the solution is neutral when equal amounts of acid and base have been mixed together. After that, the addition of a little more NaOH makes the pH basic and the solution turns pink. This is referred to as the endpoint. If we know the moles of KHP and the volume of NaOH used to neutralize it, we can calculate the exact concentration of the base.
Once we have a standardized base, we can determine the pKa of an acid by titrating a known concentration of the acid with our standardized base while monitoring the pH. The plot of pH versus the volume of base added is called a titration curve. The curve usually follows an S or sigmoidal shape, where the inflection point of the steepest part of the curve denotes an equivalence point.
Here, the moles of hydroxide ions and dissociated hydrogen ions are equal. Like pKa, we'll see one equivalence point for each dissociated hydrogen ion. So, a monoprotic acid has only one equivalence point, and a triprotic acid has three.
When we perform the titration, we will know that we have passed the equivalence point when the pH indicator just barely turns from colorless to pink. This is called the titration endpoint. Like when we standardize the base, this is when the solution has a small excess of hydroxide ions and thus is slightly basic.
Another inflection point in the graph occurs halfway to the equivalence point. Here, the concentrations of the dissociated and non-dissociated acids are equal. Thus, the pH at this point is equal to the pKa. So, if we perform a titration and determine the equivalence point volume, then we can calculate pKa as the pH at half of this volume.
In this lab, you'll first standardize your base and then perform a titration using that standardized base to determine two pKa’s of a polyprotic acid.
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Q1: What is the difference between acid strength and pH?
pH measures the concentration of hydrogen ions in a solution on a logarithmic scale from 0 to 14, where values below 7 are acidic and above 7 are basic. Acid strength, however, refers to how readily hydrogen ions dissociate from the acid molecule. Two acids can have different pH values but similar strength, or vice versa. Strength is quantified using the acid dissociation constant, Ka, or its logarithmic form, pKa.
Q2: How does pKa relate to acid strength?
pKa is the negative logarithm of the acid dissociation constant, Ka. Lower pKa values indicate stronger acids because the hydrogen ion dissociates more readily from the conjugate base. Higher pKa values correspond to weaker acids that dissociate less completely. This inverse relationship makes pKa a convenient way to compare acid strength across different compounds.
Q3: What is the difference between monoprotic and polyprotic acids?
Monoprotic acids, like hydrochloric acid, can dissociate only one hydrogen ion and have a single pKa value. Polyprotic acids, such as phosphoric acid, can dissociate multiple hydrogen ions sequentially, with each dissociation having its own distinct pKa value. During titration, polyprotic acids produce multiple equivalence points, one for each hydrogen ion released.
Q4: Why must a base be standardized before titration?
A standardized base solution has a precisely known concentration, which is essential for accurate titration calculations. Sodium hydroxide, commonly used as a titrant, is hygroscopic and absorbs water from the atmosphere, making its actual concentration lower than expected. To determine the exact concentration, the base is first titrated against a non-hygroscopic acid like potassium hydrogen phthalate with a known concentration.
Q5: What does the equivalence point represent in a titration curve?
The equivalence point occurs when the moles of hydrogen ions from the acid equal the moles of hydroxide ions added from the base, resulting in a neutralization reaction that forms salt and water. On a titration curve, it appears at the inflection point of the steepest section. For polyprotic acids, multiple equivalence points exist, one for each hydrogen ion dissociation.
Q6: How can you determine pKa from a titration curve?
The pH at the halfway point to the equivalence point equals the pKa of the acid. At this midpoint, the concentrations of the dissociated and non-dissociated acid forms are equal. By identifying the equivalence point volume on the titration curve and measuring the pH at half that volume, you can directly read the pKa value without additional calculations.
Q7: How does phenolphthalein indicate the endpoint of a titration?
Phenolphthalein is a pH indicator that remains colorless in acidic solutions (pH 0-8) and turns pink in basic solutions. During titration, as the base neutralizes the acid and pH increases past the equivalence point, phenolphthalein changes from colorless to light pink. This permanent color change signals the endpoint, indicating a slight excess of hydroxide ions and completion of the titration.