Question

The \(\mathrm{pH}\) of a particular raindrop is 5.6. (a) Assuming the major species in the raindrop are \(\mathrm{H}_{2} \mathrm{CO}_{3}(a q), \mathrm{HCO}_{3}^{-}(a q),\) and \(\mathrm{CO}_{3}^{2-}(a q),\) calculate the concentrations of these species in the raindrop, assuming the total carbonate concentration is \(1.0 \times 10^{-5} \mathrm{M}\). The appropriate \(K_{a}\) values are given in Table 16.3. (b) What experiments could you do to test the hypothesis that the rain also contains sulfur-containing species that contribute to its pH? Assume you have a large sample of rain to test.

Short answer

In summary, the concentrations of the major carbonate species in the raindrop with pH 5.6 are [H2CO3] ≈ \(9.1 \times 10^{-6} M\), [HCO3-] ≈ \(9.0 \times 10^{-6} M\), and [CO3^2-] ≈ \(1.0 \times 10^{-10} M\). To test for the presence of sulfur-containing species in the rain, possible experiments include Ion Chromatography (IC) for quantitative analysis, qualitative tests using barium chloride or potassium permanganate solutions for sulfate and sulfite ions, respectively.

Step-by-step solution

Write the given information and equilibrium equations

We are given the following information: - pH of the raindrop = 5.6 - Total carbonate concentration = \(1.0 \times 10^{-5} M\) - Equilibrium constants (K_a) for H2CO3 and HCO3- (Table 16.3) We need to find the concentrations of H2CO3, HCO3-, and CO3^2-. Write the equilibrium equations for the relevant reactions: 1. \(H_2CO_3 \leftrightarrows H^+ + HCO_3^-\) with equilibrium constant \(K_{a1}\) 2. \(HCO_3^- \leftrightarrows H^+ + CO_3^{2-}\) with equilibrium constant \(K_{a2}\)

Calculate the concentration of H+ ions

We have the pH value, so we can find the concentration of H+ ions: \(pH = -\log[H^+]\) Solve for [H+]: \([H^+] = 10^{-5.6} M\)

Write the equilibrium expressions and assumptions

Write the equilibrium expressions for the two reactions: \(K_{a1} = \frac{[H^+][HCO_3^-]}{[H_2CO_3]}\) \(K_{a2} = \frac{[H^+][CO_3^{2-}]}{[HCO_3^-]}\) From Table 16.3, we have \(K_{a1} = 4.45 \times 10^{-7}\) and \(K_{a2} = 4.69 \times 10^{-11}\). Assume that the concentration of H2CO3 is much greater than the concentration of CO3^2-, so: Total carbonate concentration ≈ [H2CO3] + [HCO3^-]

Solve for the concentrations of the species

Using the assumed relationship: \(1.0 \times 10^{-5} M = [H_2CO_3] + [HCO_3^-]\) Now, we have equations for K_a1 and K_a2 in terms of the concentrations. We can substitute [H+] from Step 2 and solve the equations simultaneously to find the concentrations of the three species: 1. \(4.45 \times 10^{-7} = \frac{10^{-5.6} [HCO_3^-]}{[H_2CO_3]}\) 2. \(4.69 \times 10^{-11} = \frac{10^{-5.6} [CO_3^{2-}]}{[HCO_3^-]}\) Solving these equations simultaneously, we obtain: [H2CO3] ≈ \(9.1 \times 10^{-6} M\) [HCO3-] ≈ \(9.0 \times 10^{-6} M\) [CO3^2-] ≈ \(1.0 \times 10^{-10} M\)

Suggest experiments to test for sulfur-containing species

To test for the presence of sulfur-containing species in the rain, such as sulfuric acid (H2SO4) or sulfurous acid (H2SO3), some possible experiments include: 1. Conduct a quantitative analysis using Ion Chromatography (IC) to detect and measure the concentrations of sulfate (SO4^2-) and sulfite (SO3^2-) ions in the rain sample. 2. Perform a qualitative test for sulfate ions using a barium chloride solution. Add a few drops of barium chloride solution to the rain sample, and observe if a white precipitate of barium sulfate (BaSO4) forms, indicating the presence of sulfate ions. 3. Carry out a similar qualitative test for sulfite ions using potassium permanganate solution. When added to a solution containing sulfite ions, the purple color of potassium permanganate solution will fade due to reduction, indicating the presence of sulfite ions. By performing these experiments, we can determine the presence of sulfur-containing species in the raindrop that may contribute to its pH.

Key concepts

Equilibrium Constants

Equilibrium constants (\( K_a \)) are vital in understanding chemical reactions involving acids and bases. They give insight into the extent of a reaction at equilibrium, indicating how far the reaction proceeds before reaching balance. In the case of carbonate species in a raindrop, the equilibrium reactions involved are:

• \( H_2CO_3 \leftrightarrows H^+ + HCO_3^- \) with equilibrium constant \( K_{a1} \)
• \( HCO_3^- \leftrightarrows H^+ + CO_3^{2-} \) with equilibrium constant \( K_{a2} \)

These constants are defined separately for each dissociation step of carbonic acid (\( H_2CO_3 \)). Thus, understanding these reactions and their respective constants helps predict and calculate the resting concentrations of various ions once equilibrium is reached. Given values for \( K_{a1} \) and \( K_{a2} \) are essential inputs for calculating further specifics, such as the concentration of different chemical entities in a sample.

pH Calculations

pH calculations are fundamental in determining the acidic or basic nature of a solution. pH is the negative logarithm of the hydrogen ion concentration \( ([H^+]) \).
This can be expressed as:

• pH = -log\( [H^+] \)

For the raindrop with a pH of 5.6, the hydrogen ion concentration, \( [H^+] \), can be calculated as:
\( [H^+] = 10^{-5.6} \; \text{M} \).
This step is crucial as it aids in understanding the existing acid strength within the rain. Lower pH values signify higher acidic presence, implying greater concentrations of hydrogen ions.

Carbonate Species Concentration

The concentrations of carbonate species, such as \( H_2CO_3 \), \( HCO_3^- \), and \( CO_3^{2-} \), are derived using equilibrium constants and the total known concentration of carbonates.
Initially, the given total carbonate concentration is \(1.0 \times 10^{-5} \; \text{M} \).
The first step involves the assumption that \( [H_2CO_3] + [HCO_3^-] \approx \text{Total Carbonate Concentration} \).

• This helps in setting up initial equations for solving.
• You then insert your equilibrium sets (\( K_{a1} \) and \( K_{a2} \)) to solve.

After calculation, we find:

• \([H_2CO_3] \approx 9.1 \times 10^{-6} \; M\)
• \([HCO_3^-] \approx 9.0 \times 10^{-6} \; M\)
• \([CO_3^{2-}] \approx 1.0 \times 10^{-10} \; M\)

These values outline the distribution of carbonate species within the solution at equilibrium.

Sulfur-Containing Species Detection

Detecting sulfur-containing species in rain, such as sulfuric acid (\( H_2SO_4 \)) or sulfurous acid (\( H_2SO_3 \)), is a key experiment in environmental chemistry.
These species may decrease the pH beyond the expected values due to their strong acidic nature.

• Quantitative analysis using Ion Chromatography (IC) allows for the detection and measurement of sulfate and sulfite ion concentrations accurately.
• Qualitative tests can also offer preliminary information:
  • Using barium chloride solution can highlight sulfate ions by forming a white precipitate of barium sulfate.
  • Potassium permanganate can be used to detect sulfite ions, indicated by a color change from purple to clear.

Using these methods allows a comprehensive understanding of the sulfur chemistry in rain, providing insights into potential sources of acidity and helping formulate environmental strategies to address acid rain impacts.