Question

\(\mathrm{HClO}_{4}\) is a stronger proton donor than \(\mathrm{HNO}_{3}\), but in water both acids appear to be of equal strength; they are both \(100 \%\) ionized. Why is this so? What solvent property would be necessary in order to distinguish between the acidities of these two Brønsted-Lowry acids?

Short answer

In water, \(\mathrm{HClO}_{4}\) and \(\mathrm{HNO}_{3}\) appear to be of equal strength because water is highly polar and stabilizes ions, causing both acids to fully ionize. A less polar solvent with a lower dielectric constant is required to distinguish their acidities.

Step-by-step solution

Understanding Acid Strength

Acid strength refers to an acid's ability to donate a proton to a base. In a solvent like water, strong acids are completely ionized due to the high polarity and ability of water molecules to stabilize the ions. Because water is a very polar solvent with a high dielectric constant, it can effectively stabilize ions in solution, which leads to complete ionization of strong acids.

Limitation of Water as a Solvent for Measuring Relative Acid Strengths

In water, both \(\mathrm{HClO}_{4}\) and \(\mathrm{HNO}_{3}\) appear equally strong because they are both completely ionized in water, which masks their true relative strengths. Water is leveling the playing field by being such a good solvent for ions, so even though \(\mathrm{HClO}_{4}\) is inherently a stronger proton donor, this cannot be differentiated in water.

Required Solvent Property to Differentiate Acidities

To differentiate between the acid strengths of \(\mathrm{HClO}_{4}\) and \(\mathrm{HNO}_{3}\), a less polar solvent with a lower dielectric constant is required. Such a solvent would not stabilize ions as strongly as water, thereby not fully ionizing weaker acids, which allows for a distinction in the degree of ionization based on the inherent acid strength.

Key concepts

Proton Donor

The term proton donor is key to understanding the nature of acids in a chemical setting. In essence, an acid is considered a proton donor if it can release a hydrogen ion (\textbf{H}^+), which is simply a hydrogen atom that has lost its electron and is hence just a proton. This act of donating a proton is what characterizes many acid-base reactions.

Within the context of the given exercise about the acid strength of \textbf{HClO}\(_4\) (perchloric acid) and \textbf{HNO}\(_3\) (nitric acid) in water, both compounds act as potent proton donors. When dissolved in water, these acids readily give up their protons to water molecules, generating hydronium ions (\textbf{H}\(_3\)\textbf{O}^+) and their respective negative ions, chloride (\textbf{ClO}\(_4^-\)) for perchloric acid and nitrate (\textbf{NO}\(_3^-\)) for nitric acid. However, despite perchloric acid being a stronger proton donor by nature, in water, they both appear to donate protons equally due to the solvent characteristics of water, which leads us to the role of the solvent in acid-base chemistry.

Brønsted-Lowry Acids

The exercise draws upon the Brønsted-Lowry acid-base theory, which recognizes acids as proton donors and bases as proton acceptors. This theory helps in explaining why substances like \textbf{HClO}\(_4\) and \textbf{HNO}\(_3\) behave as strong acids in water. Because the Brønsted-Lowry concept relies on the transfer of protons, the strength of an acid is measured by how effectively it donates protons to other substances.

In the context of our problem, despite the inherent differences in their acid strengths, water serves as such an efficient proton acceptor that it masks any difference between the two acids' proton donating capabilities. This highlights the limitation of using water as a solvent to measure the true strength of acids, which is why alternative solvents are sometimes required to properly differentiate between the acid strengths.

Solvent Polarity

The polarity of a solvent is a critical concept in understanding the behavior of acids in solution. Solvent polarity refers to the distribution of electrical charge within its molecules. A polar solvent like water has a marked separation of positive and negative charges, enabling it to dissolve ionic compounds effectively.

The high solvent polarity of water allows it to stabilize the ions created when an acid donates a proton. This polarity is so effective that it can fully ionize strong acids, forcing them to release all their protons. As mentioned in the exercise, this complete ionization levels the playing field for strong acids in water, which impedes distinguishing their true relative strength. To observe the differences between the acid strengths of \textbf{HClO}\(_4\) and \textbf{HNO}\(_3\), you would need a solvent with lower polarity that won't ionize all acids to the same degree.

Dielectric Constant

The dielectric constant of a solvent is intimately related to its ability to diminish the electrical force between charged particles and thus affects the degree to which it can separate charged species, such as ions in a solution. A high dielectric constant indicates a solvent that can greatly reduce the electrostatic forces between ions, which is why water, with a dielectric constant of around 80 at room temperature, is exceptional at keeping ions apart and preventing them from recombining.

This characteristic allows water to stabilize the hydronium and anion formed when strong acids ionize. In the case of our two strong acids, water's high dielectric constant means it's virtually impossible to differentiate their acidity in aqueous solution because it supports complete ionization of both. To truly determine the relative acid strengths of \textbf{HClO}\(_4\) and \textbf{HNO}\(_3\), it would be necessary to employ a solvent with a lower dielectric constant, which wouldn't be as effective at stabilizing ions and could allow us to observe varying degrees of ionization reflective of each acid's strength.