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Principles of Buffers

1) Buffers resist changes in pH when acids or bases are added. They work by having both the acid and conjugate base forms of a weak acid or weak base present in solution. 2) The pH of a buffer solution can be calculated using the Henderson-Hasselbalch equation, which relates the pH to the ratio of the concentrations of the conjugate base and acid forms. 3) Buffer capacity, or the ability to resist pH changes when acids or bases are added, depends on the concentrations of the buffer components and how close the pH is to the pKa of the buffering species. Higher concentrations and pH values near pKa result in greater buffer capacity.

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Luluin Latifa Nissa
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101 views

Principles of Buffers

1) Buffers resist changes in pH when acids or bases are added. They work by having both the acid and conjugate base forms of a weak acid or weak base present in solution. 2) The pH of a buffer solution can be calculated using the Henderson-Hasselbalch equation, which relates the pH to the ratio of the concentrations of the conjugate base and acid forms. 3) Buffer capacity, or the ability to resist pH changes when acids or bases are added, depends on the concentrations of the buffer components and how close the pH is to the pKa of the buffering species. Higher concentrations and pH values near pKa result in greater buffer capacity.

Uploaded by

Luluin Latifa Nissa
Copyright
© © All Rights Reserved
Available Formats
Download as PDF, TXT or read online on Scribd
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Principles of Buffers

buffer--a solution that resists pH change---

Important for many reactions---e.g., enzymatic methods


of analysis, etc.---

ammonia is a base---so pH will increase


as reaction proceeds; unless soln is buffered!
If instead of adding weak acid to solution---we add given
concentrations of both the acid and its conjugate base---we
create a buffer!!

HA <------> H+ + A- pKa = 4.00

pKbA- = 10.00
add 0.1 M
add 0.1 M
of metal ion salt
for forward dissociation reaction---we can calculate fraction
of dissociation--in absence of A- added--

x2 / (F-x) = 10-4 ; x = 3.1 x 10-3 (by quadratic or succ. approx.)

[A-] = [H+] = 3.1 x 10-3 M ; fraction dissociated = 0.0031/0.1 = 0.031


or 3.1%
if soln was made with 0.1 M NaA only -fraction associated = 3.2 x 10-5
so --basic chemical instincts tell you that very little changes
when you add the two species together to water--to make the
solution 0.1 M with respect the acid and the conjugate anionic base
and then wait for equilibrium!!

Key to understanding what the pH of this solution would be---is


the Henderson-Hasselbalch Eqn.
[H + ][A − ]
Ka =
[HA]
take logarithm of both sides:
 [H + ][A − ]  + [A− ]
log K a = log = log[H ] + log
 [HA]  [HA]
swap--logKa and log[H+] to opposite sides of eqn:
[HA]
− log Ka = − log[H + ] + log −
[A ]
[A − ]
pK a = pH + log HH-eqn.
[HA]
If you want to make buffer using weak base (B) and a salt of its
conjugate acid (BH+)----same basic equation applies:

[B]
pH = pK a + log +
[BH ] pKa of this conjugate
acid used in equation!

Whether using weak acid or weak base conjugate pairs to create


buffer---the pH of the final buffer solution is controlled by ratio
of the two species you add to create buffer---

• weak acid/conjugate base salt


• weak base/conjugate acid salt

back to initial problem---where we have 0.1 M HA, and 0.1 M A-


and pKa = 4.00; pH = 4.00 + log (0.1 / 0.1) = 4.00
Example problem:

Suppose you want to make a pH 5.00 buffer---using


acetic acid (HA)and sodium acetate (A-)
note: volumes
pKa of acetic acid = 4.76; cancel in log term
of HH---pH does not
What ratio of HA and A should be used? depend on volume--
only ratio of moles!-
5.00 = 4.76 + log x; where x = ([A-]/[HA]) (not always true!!!)
0.24 = log x
100.24 = x = 1.74 = ratio of moles conjugate base to acid in solution

e.g., 0.174 M sodium acetate/0.100 M acetic acid


or 0.100 sodium acetate/0.0575 M acetic acid

Concentration used of each species will determine “Buffer Capacity”


and “ionic strength” of the buffer solution!
FW=157.597 FW=121.136

very popular buffer---can obtain Tris-HCl salt, and Tris in pure forms;
what is pH of solution when 12.43 g of Tris is mixed with 4.67 g of
Tris-HCl (BH+) a diluted to 1.00 liter?

calculate molarity of each species:


[B] =[Tris] = (12.43 g/L) /(121.136 g/mol) = 0.1026 M
[BH+] = [Tris-H] =(4.67 g/L) / (157.597 g/mol) = 0.0296 M

pH= pKa +log ([B]/[BH+]) = 8.075 + log (0.1026/0.0296) = 8.61


Secret of buffers---what happens when strong acid added to
previous Tris buffer solution? ---

as you add HCl to solution--the following reaction takes place:


B + HCl -----> BH+Cl-; this decreases conc. of B and increases
concentration of BH+; this will change the ratio in the HH eqn!

suppose you add 12 mL of a 1.00 M acid; = 0.012 L x 1 M = 0.012


moles

Therefore---this will decrease the moles of B present by 0.012 moles


and increase the concentration of BH+ by 0.012 moles
0.1026 − 0.012
Hence---pH = 8.075 + log
0.0296 + 0.012
pH = 8.41-----only a change of 0.2 even though concentrated acid was
added----
If you added NaOH base--you would decrease BH+ and increase B conc.
Can also prepare buffers by starting with only one form of the two
species---and then adding a given amount of acid or base to form
the conjugate acid or base needed to provide the buffer system!

e.g., how many mL of 0.500 M NaOH should be added to 10 g of


Tris-HCl salt to yield pH of 7.60 buffer in final volume of 250 mL

how many moles of Tris-HCl = moles of BH+ = 10 g/ (157.597 g/mol)


= 0.0635 moles
for pH 7.60----HH says:
7.60 = 8.075 + log x
log x = -0.475
x = 0.335 = ratio of B moles/BH+ moles

but total moles of B + BH+ = 0.0635; then 0.335 = y/(0.0635-y)


0.0213 -0.335 y =y
y = moles of NaOH required 1.335 y= 0.0213
0.500 x V = 0.0159 ; V= 0.0318 L or 31.8 ml y=0.0159
Buffer capacity = resistance to pH change from addition of acid
or base!

•depends on concentration of buffer species---higher concentration


more buffer capacity!---a 0.10 M Tris buffer would have more
buffer capacity than a 0.01 M Tris buffer!

•depends on pH of buffer; if pH is at the pKa of the buffering species


then the buffer capacity is highest, since changes in the moles of
base in the numerator, or acid in the denominator---of HH eqn
have less effect on the log term value---when the ratio of the
fraction is 1.0! (go back to earlier problem with added HCl --same
amount, and calculate how much of a pH change would have
occurred if the buffer was initially at the pKa value!

•There is little buffer capacity when pH is > ±1.0 pH unit of the pKa

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