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The Synopsis of Buffering System-Its Chemical Review
The Synopsis of Buffering System-Its Chemical Review
The Synopsis of Buffering System-Its Chemical Review
Buffer is a solution that can effectively resist pH change upon addition of an acidic or basic component. It is able to neutralize small amounts of added acid or base, thus maintaining pH of solution relatively stable. This is important for processes &/or reactions which require specific pH ranges. Buffer solutions have a working pH range and capacity which dictate how much acid/base can be neutralized before pH changes, & amount by which it will change. 1) What is a buffer composed of? 2) How does a buffer work? 3) Selecting proper components for desired pH 4) Adding Strong Acids or Bases to Buffer Solutions 5) References 6) Contributors What is a buffer composed of? To effectively maintain a pH range, a buffer must consist of a weak conjugate acid-base pair, meaning either a. a weak acid & its conjugate base, or b. a weak base & its conjugate acid. Use of one or other will simply depend upon desired pH when preparing buffer. For example, following could function as buffers when together in solution:
Acetic acid (weak organic acid w/ formula CH3COOH) and a salt containing its conjugate base, acetate anion (CH3COO-), such as sodium acetate (CH3COONa) Pyridine (weak base w/ formula C5H5N) and a salt containing its conjugate acid, the pyridinium cation (C5H5NH+), such as Pyridinium Chloride. Ammonia (weak base w/ formula NH3) and a salt containing its conjugate acid, the ammonium cation, such as Ammonium Hydroxide (NH4OH)
When Sodium Fluoride dissolves in water, reaction goes to completion, thus we obtain: Since Na+ is conjugate of a strong base, it will have no effect on pH or reactivity of buffer. Addition of NaF to solution will, however, increase concentration of F- in buffer solution, &, consequently, by Le Chatlier's principle lead to slightly less dissociation of HF in previous equilibrium, as well. Presence of significant amounts of both conjugate acid, HF, & conjugate base, F-, allows solution to function as a buffer. This buffering action can be seen in the titration curve of a buffer solution.
As we can see, over working range of buffer. pH changes very little with addition of acid or base. Once buffering capacity is exceeded rate of pH change quickly jumps. This occurs because conjugate acid or base has been depleted through neutralization. This principle implies that a larger amount of conjugate acid or base will have a greater buffering capacity.
If acid is added:
In this reaction, conjugate base, F-, will neutralize added acid, H3O+, & this reaction goes to completion, because reaction of F- with H3O+ has an equilibrium constant much greater than one. (In fact, equilibrium constant reaction as written is just inverse of K a for HF: 1/Ka(HF) = 1/(6.6x10-4) = 1.5x10+3.) So long as there is more F- than H3O+, almost all of H3O+ will be consumed & equilibrium will shift to right, slightly increasing concentration of HF & slightly decreasing concentration of F-, but resulting in hardly any change in amount of H3O+ present once equilibrium is re-established.
If base is added:
In this reaction, conjugate acid, HF, neutralize added amounts of base, OH-, & equilibrium again shifts to right, slightly increasing concentration of F- in solution & decreasing amount of HF slightly. Again, since most of OH- is neutralized, little pH change occurs. The synopsis of buffering system-Its chemical review
These two reactions can continue to alternate back and forth with little pH change.
Example
In this example we will continue to use hydrofluoric acid buffer. We will discuss process for preparing a buffer of HF at a pH of 3.0. We can use Henderson-Hasselbalch equation to calculate necessary ratio of F- and HF. This is simply ratio of concentrations of conjugate base & conjugate acid we will need in our solution. However, what if we have 100 ml of 1 M HF & we want to prepare a buffer using NaF? How much Sodium Fluoride would we need to add in order to create a buffer at said pH (3.0)? We know from our Henderson-Hasselbalch calculation that ratio of our base/acid should be equal to 0.66. From a table of molar masses, such as a periodic table, we can calculate molar mass of NaF to be equal to 41.99g/mol. HF is a weak acid with a Ka = 6.6 x 10-4 & concentration of HF is given above as 1 M. Using this information, we can calculate amount of F- we need to add. We could use ICE tables to calculate concentration of F- from HF dissociation, but, since Ka is so small, we can approximate that virtually all of HF will remain undissociated, so amount of F- in solution from HF dissociation will be negligible. Thus, [HF] is about 1 M and [F-] is close to 0. This will be especially true once we have added more F-, addition of which will even further suppress dissociation of HF. We want ratio of Base/Acid to be 0.66, so we will need [Base]/1M = 0.66. Thus, [F-] should be about 0.66 M. For 100mL of solution, then, we will want to add 0.066 moles (0.1 L x 0.66 M) of F-. Since we are adding NaF as our source of F-, and since NaF completely dissociates in water, we need 0.066 moles of NaF. Thus, 0.066 moles x 41.99 g/mol = 2.767 g. The synopsis of buffering system-Its chemical review
Note that, since conjugate acid and conjugate base are both mixed into same volume of solution in buffer, ratio of "Base/Acid" is same whether we use a ratio of "concentration of base over concentration of acid," OR a ratio of "moles of base over moles of acid." The pH of solution does not, it turns out, depend on volume! (This is only true so long as solution does not get so dilute that auto ionization of water become an important source of H+ or OH-. Such dilute solutions are rarely used as buffers, however.)
Case-01
Suppose we needed to make a buffer solution with a pH of 2.11. In the first case, we would try and find a weak acid with a pKa value of 2.11 but At same time molarities of acid & its salt must be equal to one another. This will cause the two molarities to cancel; leaving log [A-] equal to log(1) which is zero. pH=pKa+log[A]=2.11+log(1)=2.11 This is a very unlikely scenario, however, & you won't often find yourself with Case #1
Case-02
An example: What mass of NaC7H502 must be dissolved in 0.200 L of 0.30M HC7H5O2 to produce a solution with pH = 4.78? (Assume solution volume is constant at 0.200L)
Solution:
HC7H5O2+H20 H3O++C7H5O2 Ka=6.3 105 Ka=[H3O+][C7H5O2][HC7H5O2]=6.3 105 [H3O+]=10pH=104.78=16.6106M[HC7H5O2]=0.30M[C7H5O2]= \([C_7H_5O_2^-] = K_a \times \dfrac{[HC_7H_5O_2]}{[H_3O^+]}\) 1.14M=6.3 105 0.3016.6 106 Mass = 0.200 L x 1.14 mol C7H5O2- / 1L x 1mol NaC7H5O2 / 1mol C7H5O2- x 144 g NaC7H5O2 / 1 mol NaC7H5O2 = 32.832 g NaC7H5O2