KEY

Name: ___________________________________________________________ Period: _________

Lecture 40
Buffers (AP Chemistry Topic 8.7, 8.8, 8.9, 8.10)
Student Notes

Enduring Understanding Learning Objective(s)

• A buffered solution resists changes to its pH when small • Explain the relationship between the predominant form of a
amounts of acid or base are added. weak acid or base in solution at a given pH and the pKa of the
conjugate acid or the pKb of the conjugate base.
• Explain the relationship between the ability of a buffer to
stabilize pH and the reactions that occur when an acid or a
base is added to a buffered solution.
• Identify the pH of a buffer solution based on the identity and
concentrations of the conjugate acid-base pair used to create
the buffer
• Explain the relationship between the buffer capacity of a
solution and the relative concentrations of the conjugate acid
and conjugate base components of the solution.

Buffers
buffer
Most solutions significantly change pH when an acid or base is added to them. A _______________ however
resists changes in pH
_____________________________________by neutralizing
_________________________ any added acid or base.

A buffer must contain:

weak acid AND its conjugate base

1.Significant amounts of a _________________________________________________________OR
weak base AND its
conjugate acid
2.Significant amounts of a _________________________________________________________

weak acid on its own ionizes to form

A ___________________________________________, partially
even though it __________________ _______________
does not contain sufficient base to be a
some of its conjugate base ___________________________________________________________________________
buffer
__________________________. significant
The same is true for a weak base on its own. A buffer must contain __________________
amounts
_______________of equal
the weak acid/base and its conjugate. Generally, a buffer should have ___________
concentrations
________________________ of an acid and its conjugate base and vice versa.
Note: The conjugate is usually added in the form of a _________.
salt For example, you could make a buffer
from acetic acid HC2H3O2 and its conjugate in the form of sodium acetate, NaC2H3O2 because it will
dissociate in solution to form the conjugate base, acetate, C2H3O2-

Human blood acts as a buffer composed of carbonic acid H2CO3 and its conjugate base the bicarbonate ion, HCO3-.

add a small amount

Suppose we ____________________________________ add a small
On the other hand, suppose we __________________
of strong base
_____________________________, such as NaOH, to amount of strong acid
_____________________________________________,
the solution. The carbonic acid is able to such as HCl, to the solution. The conjugate base, HCO3- is
neutralize
_____________________ the base: neutralize
able to _____________________ the added acid:

NaOH(aq) + H2CO3(aq) → H2O(l) + NaHCO3 HCl(aq) + HCO3-(aq) → Cl-(aq) + H2CO3(aq)

As long as the amount of NaOH is less than the amount As long as the amount of HCl is less than the amount of
of H2CO3 in solution, the buffer is able to neutralize the HCO3- in solution, the buffer is able to neutralize the
added NaOH and the pH change is small. added HCl and the pH change is small.

in a buffer the weak

In general, ____________________________________ in a buffer the weak base
In general, ____________________________________
,

acid neutralizes any added base

______________________________________________. neutralizes any added acid
_____________________________________________.
Recall that amphoteric substances can act as both an acid and a base. A mixture with ____________ _________________
of an _________________ ________________ can also ____________________________________.

H2PO4- is an example of an amphoteric molecule

The large number of H2PO4- molecules will be able to respond to the addition of more H+

H2PO4- (aq) + H+(aq) → H3PO4(aq)

The large number of H2PO4- molecules will be able to respond to the addition of more OH-

H2PO4- (aq) + OH-(aq) → HPO42-(aq)

Which of the following solutions is a buffer? Determine whether or not the mixing of each pair of solutions results
a. A solution that is 0.100 M in HNO2 and 0.100 M in HCl in a buffer:
b. A solution that is 0.100 M in HNO3 and 0.100 M in NaNO3 a. 0.10 M NH3 and 0.10 M NH4Cl
c. A solution that is 0.100 M in HNO2 and 0.100 M in NaCl b. 0.10 M HCl and 0.10 M NaOH
d. A solution that is 0.100 M in HNO2 and 0.100 M in NaNO2 c. 0.10 M HF and 0.10 M NaF
d. 0.10 M HCl and 0.10 M NaCl

A buffer contains significant amounts of acetic acid and sodium A buffer contains significant amounts of ammonia and ammonium
acetate. Write equations showing how this buffer neutralizes added chloride. Write equations showing how this buffer neutralizes added
acid (HCl) and added base (NaOH). acid (HCl) and added base (NaOH).

A buffer can also be created by ______________________________________________________________

__________________. The strong base reacts with the weak acid to _________________ some of it to its
_________________ _________which transforms the mixture into a ____________.
Does the mixing of 50.0 mL of 0.15 M HF and 20.0 mL of 0.15 M Determine whether or not the mixing of each pair of solutions results
NaOH result in a buffer? If so, what is the concentration of acid and in a buffer
conjugate base after mixing?
a. 150.0 mL of 0.10 M HF; 135.0 mL of 0.175 HCl

b. 165.0 mL of 0.10 M HF; 135.0 mL of 0.050 KOH

c. 105.0 mL of 0.15 M CH3NH2; 95.0 mL of 0.10 M HCl

d. 125.0 mL of 0.15 M NH3; 150.0 mL of 0.20 M NaOH

The Henderson-Hasselbalch Equation

We can derive an equation that relates the _______________________________________to the initial concentration of
the buffer components which simplifies the calculation of the pH of the buffer solution.

This equation is known as the Henderson-Hasselbalch equation

 Calculate the pH of a buffer solution that is 0.250 M in HCN and Calculate the pH of a buffer solution that is 0.050 M in benzoic acid
0.170 M in KCN. (HC7H5O2) and 0.150 M in sodium benzoate (NaC7H5O2).

Calculate the ratio of NaF to HF required to create a buffer with pH = What mass of sodium benzoate should you add to 150.0 mL of a 0.15
4.00. M benzoic acid to obtain a buffer with a pH of 4.25? Assume no
volume changes.

pH and pKa

The Henderson-Hasselbalch equation can help us establish some relationships relating to the
____________________________________________________ _____________________solution at
_____________________:

• If ____________, then log([base]/[acid]) must be negative, so ___________________

• If ____________, then log([base]/[acid]) must be zero, so ___________________

• If ____________, then log([base]/[acid]) must be positive, so ___________________

A (potentially) quicker rule of thumb:

**Logarithm Reminders**
•_______________ favors _________, so [acid] > [base]
*log of a number < 1 is negative
•_______________ favors _______________, so [acid] = [base]
*log of 1 = zero
•_______________ favors _________, so [base] > [acid]
*log of a number > 1 is positive

A buffer contains the weak acid HA and its conjugate base A-. The weak acid has a pKa of 4.82 and the buffer has a pH of 4.25.
Which statement is true about the relative concentrations of the weak acid and conjugate base in the buffer?

a. [HA] > [A-]

b. [HA] < [A-]

c. [HA] = [A-]

Recall that a difference in 1 pH unit represents a 10x difference in [H3O+].

•If pH = pKa + 1 then [base]/[acid] = 101 and there is __________________________________

•If pH = pKa + 2 then [base]/[acid] = 102 and there is __________________________________

•For example, the pKa of acetic acid is 4.74. If the pH of a buffer of acetic acid & sodium acetate was 5.74, there is
10x more acetate than acetic acid. If the pH of the buffer was 6.74, there is 100x more acetate than acetic acid.

Similarly,

• pH = pKa - 1 then [base]/[acid] = 10-1 and there is __________________________________

• pH = pKa - 2 then [base]/[acid] = 10-2 and there is __________________________________

The Henderson-Hasselbalch equation can be Use the Henderson-Hasselbalch equation to calculate the pH of a buffer
easily modified to work for a buffer formed solution that is 0.50 M in NH3 and 0.20 M in NH4Cl.
from a weak base and its conjugate acid, but,
this time, we would be calculating
_________________.
Use the Henderson-Hasselbalch equation to calculate the pH of a buffer
solution that contains 0.785% C5H5N by mass and 0.985% C5H5NHCl by mass.

Once pOH has been calculated, pH = 14 -

pOH

Calculate the ratio of CH3NH2 to CH3NH3Cl concentration required to What mass of ammonium chloride should you add to 2.55 L of 0.155
create a buffer with pH = 10.24? M NH3 to obtain a buffer with a pH of 9.55? Assume no volume
change.

Calculating the pH Change in a Buffer Solution after the Addition of a Small Amount of Strong Acid or Base
When acid or base is added to a buffer, the buffer resists a pH change. However, the pH does change by a small amount.

We can calculate the pH change by breaking the problem into 2 parts:

1.The _____________________ ____________________- use the stoichiometry of the neutralization equation to

calculate the ____________________________of the buffer components upon addition of the acid or base.

2.The _____________________ ____________________-use the new amounts of buffer components to work an

equilibrium problem to find pH. (This can be done with the ____________________________________________).

A 1.0 L buffer solution contains 0.100 mol HC2H3O2 and 0.100 mol NaC2H3O2.

1.Calculate the pH of the buffer solution.

2.Calculate the new pH after adding 0.010 mol of solid NaOH to the buffer.

3.For comparison, calculate the pH after adding 0.010 mol of solid NaOH to 1.0 L of pure water. Ignore any small
changes in volume that might occur upon addition of the base.
 Calculate the initial pH of 250.0 mL of a buffer solution that is 0.255 M in CH 3CH2NH2 and 0.235 M in CH3CH2NH3Cl. Then find the pH after the
addition of 0.010 mol of NaOH.

Calculate the initial pH of 100.0 mL of a buffer solution that is 0.175 M in HClO and 0.150 M in NaClO. Then find the pH after the addition of
150.0 mg of HBr.

Calculate the initial pH of a 250.0 mL buffer solution that is 0.250 M acetic acid and 0.250 M sodium acetate. What is the pH after the addition
of 0.0050 mol of HCl? What is the pH after the addition of 0.0050 mol of NaOH?

Summary

When you calculate the pH of a buffer after adding small amounts of acid or base, remember the following:

•Adding a small amount of strong acid to a buffer converts a stoichiometric amount of the base to the conjugate acid
decreasing the pH of the buffer. (adding acid decreases pH just as we would expect).

•Adding a small amount of strong base to a buffer converts a stoichiometric amount of the acid to the conjugate base
and increases the pH of the buffer (adding base increases the pH just as we would expect).

Buffer Capacity and Buffer Range

An ___________________ _____________ neutralizes small to moderate amounts of added acid or base, but a buffer
can be destroyed by the addition of too much acid or too much base.

There are two factors that can influence the effectiveness of a buffer:

1.The ________________ _________________of the acid and conjugate base

2.The ________________ ______________________of the acid and conjugate base

_____________ ________________ is defined as the amount of acid or base that you can add to a buffer without
causing a large change in pH. Generally, the pH should not change by more than 1 unit.

_____________ ____________ refers to the pH range over which an acid and its conjugate base can be effective. The
effective range for a buffering system is one pH unit on either side of pKa.
 Consider the following buffers composed of HA and A- for which the pKa = 5.00; both buffers have a total of 0.20 mol of total acid and
conjugate base. Buffer A has 0.10 mol of HA and A-. Buffer B has more acid than base with 0.18 mol HA and 0.020 mol A -. Calculate the initial
pH of both solutions. Then calculate the pH of each solution after the addition of 0.010 mol NaOH for each buffer. What is the percent change
in pH for each of the buffers?

Key Takeaway: Relative Amounts of Acid and Base

A buffer with _____________________________________________________________________________________

and is therefore a more effective buffer.

A buffer becomes less effective as the difference in relative amounts of acid and conjugate base increases.

Again, consider the generic buffer composed of HA and A- with a pKa of 5.00. Buffer C has 0.050 M HA and 0.050 M A-. Buffer D
has 0.50 M HA and 0.50 M A-. Calculate the initial pH of both solutions. Then calculate the pH of each solution after the addition of
0.010 mol NaOH to each solution. What is the percent change in pH for each of the buffers?

Key Takeaway: Absolute Concentrations of Acid and Base

The ________________________________________________________________________________________
______________________________. However, the buffer with higher concentrations is able to resist pH changes
better.

________________________________________________________________________________________________
______________________________________________.

The more dilute the buffer components, the less effective the buffer.
 Buffer Range

The effective ___________ for a buffering system is _________________________________. We can choose an

acid/conjugate base system for a buffer with a desired pH.

Which acid would you choose to combine with its sodium salt to make a solution buffered at pH 4.25?

a. Chlorous acid (HClO2) pKa = 1.95

b. Nitrous acid (HNO2) pKa = 3.34

c. Formic acid (HCHO2) pKa = 3.74

d. Hypochlorous (HClO) pKa = 7.54

Composition of the Buffer Mixture

•If ___________________ then buffer has an ___________________ ________________ to deal with the addition of
__________ions.

•Increasing concentration of acid over base means a lower pH and a lower pH range, but increases buffer capacity to
deal with OH—(aq)

•If ___________________ then buffer has an ___________________ ________________ to deal with the addition of
_________ions.

•Increasing concentration of base over acid means a higher pH and a higher pH range, but increases buffer capacity to
deal with H+(aq)