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Questions and Answers
The pKa of NaHCO3 is ______.
The pKa of NaHCO3 is ______.
10.25
In the Henderson-Hasselbalch equation, [TRIS]/[TRIS-H+] = ______ at pH 8.0.
In the Henderson-Hasselbalch equation, [TRIS]/[TRIS-H+] = ______ at pH 8.0.
0.83
The Henderson-Hasselbalch equation relates pH, pKa and acid/base ______.
The Henderson-Hasselbalch equation relates pH, pKa and acid/base ______.
concentrations
A buffer is more effective at ______ concentration.
A buffer is more effective at ______ concentration.
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Buffer solutions can consist of a weak acid and its salt (conjugate ______).
Buffer solutions can consist of a weak acid and its salt (conjugate ______).
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In buffering, addition of H3O+ is neutralized by ______ from the buffer.
In buffering, addition of H3O+ is neutralized by ______ from the buffer.
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If the pKa of benzoic acid is 4.19, what is the ratio of [PhCO2H]/[PhCO2−] necessary for pH ______?
If the pKa of benzoic acid is 4.19, what is the ratio of [PhCO2H]/[PhCO2−] necessary for pH ______?
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The weak acid AcOH has a pKa of ______.
The weak acid AcOH has a pKa of ______.
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The addition of acid to 0.1 M TRIS/TRIS-H+ results in [TRIS] = ______.
The addition of acid to 0.1 M TRIS/TRIS-H+ results in [TRIS] = ______.
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When 0.005 M H+ is added, [TRIS-H+] becomes ______ M after addition.
When 0.005 M H+ is added, [TRIS-H+] becomes ______ M after addition.
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The pH of a buffer solution can only be reduced slightly with the addition of a very strong ______.
The pH of a buffer solution can only be reduced slightly with the addition of a very strong ______.
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Common buffers include NaH2PO4 / Na2HPO4 in the pH range of ______.
Common buffers include NaH2PO4 / Na2HPO4 in the pH range of ______.
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Before adjustment, the concentration of [TRIS] when 0.02 M TRIS/TRIS-H+ is used is ______ M.
Before adjustment, the concentration of [TRIS] when 0.02 M TRIS/TRIS-H+ is used is ______ M.
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HNO3 is a very strong acid, fully dissociated into ______ and NO3-.
HNO3 is a very strong acid, fully dissociated into ______ and NO3-.
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The value of pH is calculated using the formula pH = pKa − log10(/).
The value of pH is calculated using the formula pH = pKa − log10(/).
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The ratio of TRIS to TRIS-H+ at a pH of 8.0 involves the use of pKa which is ______.
The ratio of TRIS to TRIS-H+ at a pH of 8.0 involves the use of pKa which is ______.
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The behavior of ions in solution is affected by the degree of ______.
The behavior of ions in solution is affected by the degree of ______.
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In pharmaceutical solutions, real behavior is crucial to consider rather than ideal ______.
In pharmaceutical solutions, real behavior is crucial to consider rather than ideal ______.
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Buffer solutions consisting of KH2PO4 / K2HPO4 have a desired pH range of ______.
Buffer solutions consisting of KH2PO4 / K2HPO4 have a desired pH range of ______.
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The buffering effect can be diminished if the addition of acid reaches equal or greater ______ than the buffer concentration.
The buffering effect can be diminished if the addition of acid reaches equal or greater ______ than the buffer concentration.
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The activity of component i is represented as ______.
The activity of component i is represented as ______.
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The equation 𝜇𝑖 = 𝜇𝑖° + 𝑅𝑇 ln ______ quantifies deviations from ideality.
The equation 𝜇𝑖 = 𝜇𝑖° + 𝑅𝑇 ln ______ quantifies deviations from ideality.
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The Debye Huckel Limiting Law uses a constant A, which is equal to ______ for water at 25 °C.
The Debye Huckel Limiting Law uses a constant A, which is equal to ______ for water at 25 °C.
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Ionic strength, I, is calculated using the formula I = 1/2 ______.
Ionic strength, I, is calculated using the formula I = 1/2 ______.
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In the example of Na3PO4, the ionic strength I was calculated to be ______ M.
In the example of Na3PO4, the ionic strength I was calculated to be ______ M.
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The mean activity coefficient for Na3PO4 was found to be ______.
The mean activity coefficient for Na3PO4 was found to be ______.
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In the expression pKa + pKb = ______, pKw represents the ion product of water.
In the expression pKa + pKb = ______, pKw represents the ion product of water.
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To calculate mean activity a±, you first need to determine the mean ionic concentration ______.
To calculate mean activity a±, you first need to determine the mean ionic concentration ______.
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For the solution of MgCl2, the assumption is that it is fully ______ in solution.
For the solution of MgCl2, the assumption is that it is fully ______ in solution.
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The term 𝜇𝑖 corresponds to the ______ potential of component i in solution.
The term 𝜇𝑖 corresponds to the ______ potential of component i in solution.
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Study Notes
Henderson-Hasselbalch Equation
- Relates pH, pKa, and acid/base concentrations
- For bases, use the pKa of the conjugate acid
Buffer Solutions
- Solution of weak acid and its salt (conjugate base) or a weak base and its salt (conjugate acid)
- E.g., acetic acid/sodium acetate
- Acetic acid (AcOH) is weakly dissociated (pKa 4.76); sodium acetate (AcONa) is fully dissociated
Buffering Effect
- Addition of hydroxide (OH-) is neutralized by acetic acid (AcOH)
- Addition of hydronium (H3O+) is neutralized by acetate (AcO-)
- Example: 0.045 mol/L solution of AcOH and 0.045 mol/L solution of AcONa
Buffering Effect Example
- E.g., 2.25 x 10^-3 mol AcOH and AcONa
- Add 1.0 x 10^-4 mol HNO3
- AcO- + H+ → AcOH
- [AcO-] = (2.25 x 10^-3 - 1.0 x 10^-4) = 2.15 x 10^-3 mol
- [AcOH] = (2.25 x 10^-3 + 1.0 x 10^-4) = 2.35 x 10^-3 mol
Effective Buffering
- pH of the solution is reduced by the addition of acid, but not greatly reduced (from 4.76 to 4.72)
- Addition of equal or greater concentrations of added acid would break down the buffering effect
- Common buffers include NaH2PO4/Na2HPO4 (pH range 6-8), KH2PO4/K2HPO4 (pH range 6-8), TRIS (pH range 7-9), and HEPES (pH range 6.8 – 8.2)
TRIS/TRIS-H+ Buffer Worked Example
- pKa of TRIS-H+ is 8.08
- What is the TRIS/TRIS-H+ ratio at pH 8.0?
- pH = pKa + log10([TRIS]/[TRIS-H+])
- -0.08 = log10([TRIS]/[TRIS-H+])
- [TRIS]/[TRIS-H+] = 0.83
Addition of Acid to TRIS/TRIS-H+ Buffer
- Starting with 0.1 M TRIS/TRIS-H+ buffer:
- [TRIS] + [TRIS-H+] = 0.1 M
- [TRIS]/[TRIS-H+] = 0.83
- [TRIS] = 0.83[TRIS-H+]
- [TRIS-H+] = 0.055 M
- [TRIS] = 0.045 M
- Adding 0.005 M H+:
- [TRIS] = 0.040 M
- [TRIS-H+] = 0.060 M
- pH = pKa - log10([TRIS-H+]/[TRIS]) = 7.9
Addition of Acid to 0.02 M TRIS/TRIS-H+ Buffer
- Starting with 0.02 M TRIS/TRIS-H+ buffer:
- [TRIS] + [TRIS-H+] = 0.02 M
- [TRIS]/[TRIS-H+] = 0.83
- [TRIS] = 0.009 M
- [TRIS-H+] = 0.011 M
- Adding 0.005 M H+:
- [TRIS] = 0.004 M
- [TRIS-H+] = 0.016 M
- pH = pKa - log10([TRIS-H+]/[TRIS]) = 7.48
- Buffers are more effective at higher concentrations
Ions in Solution
- Behavior of ions in solutions is affected by:
- Degree of ionization
- Extent of solvation
- Ion-ion vs. ion-solvent interactions
- External fields
- Other phenomena
- In pharmaceutical solutions, consider the effect of dissolved ions
- Consider real (rather than ideal) behavior: activity rather than concentration
Activity of Ions in Solution
- Activity (ai) quantifies deviations from ideality
- μi = μi° + RT ln ai
- ai = γi[i], where:
- γi is the activity coefficient of component i
- μi = μi° + RT ln [i] + RT ln γi
Activity Coefficient
- log10 γ± = -Az+z-√I
- Debye-Hückel Limiting Law
- A is a constant (0.509 for water at 25 °C)
- z+ and z- are the charges of the positive and negative ions
- '±' implies mean value for both ions
- I is the Ionic Strength
Ionic Strength (I)
- Depends on the number of cations and anions in solutions
- Quantifies the ionic field generated by a system of ions in solution
- I = ½ Σi zi²[i]
Ionic Strength and Mean Activity Coefficient Worked Example: 0.1 M Na3PO4
- Na3PO4 fully dissociates in water to 3Na+ and PO43-
- zNa = 1; [Na] = 3 x 0.1 M
- zPO4 = 3; [PO4] = 0.1 M
- I = ½{[(0.3M)12] + [(0.1M)32]} = 0.60 M
- log10ϒ± = −(0.509)(1)(3)√(0.6) = − 1.183
- ϒ± = 0.066
Mean Activity of 0.1 M Na3PO4
- a± = ϒ±[±] ([±] = mean ionic concentration of salt)
- [±] = n√{([+])n+([-])n-} n = n+ + n-
- For Na3PO4, [±] = 4√{(0.3)3(0.1)} = 0.228 M
- a± (Na3PO4) = (0.066)(0.228 M) = 0.015 M
- There is a significant difference between ionic activity and concentration
- Activities determine equilibria for ions in solution
Ka, Kb and Kw
- Note: AH and A- correspond to the acid and conjugate base (or corresponding base and conjugate acid)
- pKa + pKb = pKw
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Description
This quiz covers the concepts of buffer solutions and the Henderson-Hasselbalch equation, exploring how pH, pKa, and concentrations of acids and bases relate. It also examines the buffering effect, including examples using acetic acid and sodium acetate. Test your understanding of these key concepts in chemistry!