Experiment 8: Acids, Bases, Salts, and Buffers

GOAL AND OVERVIEW

Hydrolysis of salts will be used to study the acid-base properties of dissolved
ions in aqueous solutions. The approximate pH of these solutions will be
determined using acid-base indicators. A buffer solution will be prepared, and its
ability to moderate pH will be investigated alongside solutions that cannot function
as buffers.

Objectives of the data analysis

 understand conjugate acid-base pairs and equilibria of weak acids and bases
 perform calculations involving ionic equilibria
 understand the components of buffer solutions and how they work to resist
changes in pH

SUGGESTED REVIEW AND EXTERNAL READING

 reference section on data analysis; relevant textbook information on acids,
bases, salts, and buffers

BACKGROUND
Aqueous solutions of substances such as HCl (hydrochloric acid) or HC2H3O2
(acetic acid) are expected to be acidic ([H3O+] > [OH-], pH < 7), while aqueous
solutions of substances such as NaOH (sodium hydroxide) or NH3(ammonia) are
expected to be basic ([H3O+] < [OH-], pH > 7).
Recall that Brønsted-Lowry acids are proton donors and bases are proton
acceptors. In water, an acid can donate a proton to water to form H3O+ and the
conjugate base; a base can accept a proton from water to form OH- and the
conjugate acid. Also, when an acid and base undergo a neutralization reaction, the
products usually include water and a “salt”. For example,
HCl(aq) + NaOH(aq) → H2O(l) + NaCl(aq)

It may be surprising to discover that the dissolution of some salts into water can
affect the pH. For example, aqueous solutions of NaNO2 and KC2H3O2 are basic,
whereas those of NH4Cl and FeCl3 are acidic. Many salts are strong electrolytes
and exist as ions in aqueous solutions. It is the dissolved ions that have the
potential to undergo proton transfers with water to generate H3O+ or OH-. These
reactions are sometimes called hydrolysis reactions (or proton transfer
reactions).
Anions such as C2H3O2- or OCl- that are the conjugate bases of weak acids
(HC2H3O2 or HOCl) react
with water to form OH-. Cations such as Cr3+ or NH4+ come from weak bases and
react to form H3O+.

A weak acid is one which does not completely dissociate in or react with the
water solution. Instead, this equilibrium is established. The equilibrium constant is
called the acid dissociation constant and is given the symbol, Ka.
HA(aq) + H2O(l)  A-(aq) + H3O+(aq) or HA(aq)  A-(aq) + H+(aq)

83
 (1)
[ H 3O + ][ A − ] [ H + ][ A − ]
Ka = Ka =
[ HA ] or [ HA ] (2)

HA represents a weak acid; A- stands for its conjugate base.

A weak base is one which does not completely dissociate in or react with the
water solution. Instead, this equilibrium is established. The equilibrium constant is
called the base dissociation constant and is given the symbol, Kb.
A-(aq) + H2O(l)  HA(aq) + OH-(aq) (3)
[ OH − ][ HA ]
Kb = (4)
[ A− ]
Looking at the behavior of the conjugate acid-base
pair HA and A- and their behavior in water:
HA(aq)  A-(aq) + H+(aq) (1)
A (aq) + H2O(l)  HA(aq) + OH (aq)
- -
(3)
the net ionic equation is: H (aq) + OH (l)  H2O(l)
+ -

[ H + ][ A − ] [ HA ][OH − ]
and: K aK b = × −
= [ H + ][ OH − ] = K w
[ HA ] [A ]

Kw at 25oC is 1.0× 10-14. This relationship allows you to find Kb for the conjugate
base of a weak acid or Ka for the conjugate acid of a weak base.

The stronger an acid is, the larger its Ka and the weaker its conjugate base (with
a smaller Kb). Likewise, the weaker an acid is, the smaller its Ka and the stronger
its conjugate base (with a larger Kb). Similar statements apply to bases and their
conjugate acids.

Hydrolysis – Anions of Weak Acids

Anion of weak acids can react with proton sources. In water, the anions react
with water to some extent to form OH- (and the conjugate acid). The OH- causes
the solution pH to be greater than 7.

For example: NO2-(aq) + H2O(l)  HNO2(aq) + OH-(aq)

Note the similarity to: NH3(aq) + H2O(l)  NH4+(aq) + OH-(aq)
K w 1.0 ×10 −14
The Ka of HNO2 is 4.5× 10 , so Kb for
-4 Kb = = = 2.2 ×10 −11 NO2- is:
Ka 4.5 ×10 −4

Compare this to the value of Kb for NH3: 1.8× 10-5. Which is the stronger base, NO2-
or NH3?

To calculate the pH of a solution containing one of these ions, you will need to
know the concentration of the H3O+ at equilibrium. The standard approach is write
the balanced chemical equation with a grid below it where rows give initial
amounts, changes in amounts, and final equilibrium amounts and concentrations.
This is an “ICE” table:
X + Y  XY

84
 I_nitial amount (mole/L) [X]initial [Y]initial 0
C_hange in amount
−x −x +x
(mole/L)
E_quilibrium amount
[X]initial −x [Y]initial −x +x
(mole/L)

 initial amounts of reactants (amounts before the reaction begins): find via
the dilution equation
 initial amount of product (the amount before the reaction begins): here,
assume zero
 equilibrium concentration of product (after equilibrium is attained): find from
pH
As an example, find the pH of 0.10 M NaOCl. Ka of HOCl is 3.0× 10-8.
OCl-(aq) + H2O(l)  HOCl(aq) + OH-(aq)
K w 1.0 ×10 −14
Kb = = −8
= 3.3 ×10 −7
Ka 3.0 ×10

OCl- + H2O  HOCl + OH-

0.10 --- 0 ~0
-x --- +x +x
0.10 - x --- x x
Kb is small, so x can be neglected relative to 0.10, so 0.10 – x ≈ 0.10
[ OH − ][ HOCl ] [ x ][ x ]
Kb = −
= 3.3 ×10 −7 =
[ OCl ] [ 0.10 ]
x = K b[ 0.10 ] = 1.8 ×10 −4 = [ OH − ]
pH = −log[H 3O+ ] = −log(1 ×10 −14 / 1.8 ×10 −4 ) = 10 .26

Anions derived from strong acids, such as Cl- from HCl or NO3- from HNO3, do not
react with water to affect pH. Br-, I-, SO42-, ClO4- are also nonbases in water
(spectator ions). The parent acids are so strong in water that the conjugate bases
are exceedingly weak.
Anions with ionizable protons such as HCO3-, H2PO4-, and HPO42- are amphiprotic
– they may be acidic or basic, depending on the values of Ka and Kb for the ion.
These types of species will not be considered in this lab.

Hydrolysis – Cations of Weak Bases

Cations derived from weak bases react with water to increase the H3O+
concentration (acidic). Consider NH4+ in water: NH4+(aq) + H2O(l)  NH3(aq)
+ H3O+(aq)
or: NH4+(aq)  NH3(aq) + H+ (aq)

Ka for NH4+, the conjugate acid of NH3, can be determined using the Kb of NH3 and
Kw:
K w 1.0 ×10 −14
Ka = = = 5.6 ×10 −10
Kb 1.8 ×10 −5

85
 Cations of the group 1A metals (Li+, Na+, K+, Rb+, Cs+) and the group 2A metals
(Ca2+, Sr2+, Ba2+) do not react with water and are nonacids. They do not affect the
pH of the solution.

Hydrated cations of many other metals do hydrolyze to produce acidic

solutions. For example:
Fe(H2O)63+(aq) + H2O(l)  Fe(H2O)5(OH)2+(aq) + H3O+(aq)
The waters of hydration are sometimes omitted: Fe(H2O)63+(aq) ≡ Fe3+(aq);
Fe(H2O)5(OH)2+(aq) ≡ Fe (OH)2+(aq).
Additional hydrolysis reactions can occur to produce species such as
Fe(H2O)4(OH)2 +(aq), even leading to the precipitation of Fe(OH)3. The equilibria of
these types of ions can be complex. The examples illustrate the acidic nature of
dipositive and tripositive ions, and most of the H+(aq) in such a solution come from
these reactions.

Summary of Hydrolysis of Salts

The acidity, basicity, or neutrality of an aqueous salt solution can be predicted
based on the strengths of the acid and base from which the salt was derived.

1. Cation from strong base; anion from strong acid Ex. NaCl, KNO3
Solution has pH = 7 (neutral)

2. Cation from weak base; anion from strong acid Ex. NH4Cl, Zn(NO3)2
Solution has pH < 7 (acidic) due to the hydrolysis of the cation.

3. Cation from strong base; anion from weak acid Ex. NaF, KNO2
Solution has pH > 7 (basic) due to the hydrolysis of the anion.

4. Cation from weak base; anion from weak acid Ex. NH4F, NH4C2H3O2
Solution pH is determined by the relative Ka and Kb of the cation and anion.

In part 1 of this experiment, the pH of water and several salt solutions will be
tested. The pH and initial concentration of each solution (and using the
approximation that the extent of dissociation is small relative to that
concentration) allows an approximate value of Ka or Kb to be calculated. A set of
acid-base indicators will be used to determine pH (see figure).
13 12.0
12 Red
Alizari
n
11 10.0 yellow
10 Red -R
Phenol- 10.1
9 8.0 phthale Yellow
7.6 Red in
8 Blue 8.2
Bromothy Pheno Colorl
7 6.0 l red
mol ess
Yellow
blue 6.6
6 Methy
4.4 6.0 Yellow
l
5 Yellow Yellow
Methy red
4 l 4.8
orang Red
3 e
3.1
2 Red
pH ↑ color changes
86
 As an example, a solution of 0.10 M NaOBr has a pH of 10.85.
This solution would appear: Yellow in methyl orange (pH > 4.4); yellow in
methyl red (pH > 6.0); blue in bromothymol blue (pH > 7.6); red in phenol red
(pH > 8.0); red in phenolphthalein (pH > 10.0), and yellow-red in alizarin
yellow-R (pH between 10.1 and 12.0).
Determine which ion hydrolyzes in water and calculate its Ka or Kb. Na+ is a
spectator ion and does not affect the pH of the solution. OBr- is the conjugate base
of a weak acid, HOBr. The hydrolysis equation is:
OBr-(aq) + H2O(l)  HOBr(aq) + OH-(aq)
The pOH of the solution is 14.00 – 10.85 = 3.15, so the [OH-] is 10-3.15 =
7.1× 10-4.
Because the [OH ] concentration derived from the OBr- hydrolysis is much
-

greater than that from the auto-ionization of water, the [OH-] is essentially equal to
[HOBr] formed. The [OBr-] concentration is not significantly changed by the
hydrolysis.
OBr- + H2O  HOBr + OH-
0.10 --- 0 ~0
−7.1× 10-4 --- +7.1× 10 -4
+7.1× 10-4
~0.10 --- 7.1× 10-4 7.1× 10-4
[ OH − ][ HOBr ] [ 7.1 ×10 −4 ][ 7.1 ×10 −4 ]
Kb = = = 5.0 ×10 −6
[ OBr− ] [ 0.10 ]
The solutions will generally be more acidic than predicted primarily due to the
presence of dissolved CO2. CO2 reacts with water to generate H3O+ (aqueous
protons, H+(aq)):
CO2(g) + H2O(l)  H2CO3(aq)  HCO3-(aq) + H+(aq)
The solubility of CO2 is greatest in basic solutions; intermediate in neutral; and
least in acidic. Boiling can help remove the CO2.

Buffer Solutions (“Buffers”)

The pH of a solution frequently needs to be controlled. The effect of the
addition of even a small amount of strong acid or strong base to water is large – for
example, the addition of 0.001 mol HCl to 1 L water causes the pH to drop from 7.0
to 3.0; the addition of 0.001 mol of NaOH to 1 L water causes the pH to rise to
11.0. These types of changes can be disastrous, particularly in biological systems.

A buffer solution resists large changes in pH upon the addition of small amounts
of strong acid or strong base. A buffer has two components: one that will react
with added H+ and one that will react with added OH-. Usually these two parts are
an acid and its conjugate base. Buffers are often prepared by mixing a weak acid
(or weak base) with a salt of that acid (or base). For example, a buffer could be
made by adding NaC2H3O2 solution to an HC2H3O2 solution. Buffers of almost any
pH can be made by proper choice of components and concentrations.

87
 If significant concentrations of both a weak acid and its conjugate base are
present in the buffer:

added OH- reacts with the weak acid: HA + OH-  H2O + A-

K1 = 1/Kb, A-
added H+ reacts with the conjugate base: A- + H+  HA
K2 = 1/Ka, HA

K1 and K2 are large, so the above reactions essentially go to completion. Once

equilibrium is again reached, HA and A- (and H2O) are the dominant species in the
solution:
[HA]
HA  H+ + A- [ H +] = Ka×
[ A- ]

The expression for [H+] indicates that the pH depends on two factors: the
value of Ka for the acid component of the buffer and the ratio of the weak acid to
its conjugate base ([HA]/[A-]).

Looking again at the equilibrium expressions above: small amounts of added

OH- would slightly increase the A- concentration; small amounts of added H+ would
slightly increase the HA concentration. As long as the ratio of [HA]/[A-] is relatively
constant, the pH change is small.

Buffers work most effectively when [HA]/[A-] is roughly equal to 1 ([HA] ≈ [A-]).
When [HA] equals [A-], [ A- ] [H+] equals Ka:
K a =[ H + ] =[ H + ] ×1 = [ H + ]
[HA]

Since pH is usually of interest, the Ka expression is rearranged to give the

Henderson-Hasselbach [ A − ] equation:
pH = pKa + log
[ HA ]
(5)

Eq. 5 is particularly useful for calculating the pH of a buffer, particularly since

the small amounts of acid or base that ionize can normally be ignored. Thus, the
initial concentrations of HA and A- can be used directly in Eq. 5.

As an example, find the pH of a buffer that is 0.150 M lactic acid (HC3H5O3,

“HLc”) and 0.130 M sodium lactate (NaC3H5O3, “NaLc”). Ka for HLc = 1.4× 10-4.

HLc-(aq)  H+(aq) + Lc-(aq

0.150 ~0 0.130
-x +x +x
~0.150 x ~0.130
[ A− ] [ 0.130 ]
pH = pKa + log = 3.85 + log = 3.85 − 0.062 = 3.79
[ HA ] [ 0.150 ]

88
Addition of strong acid or base to buffers
When strong acid is added to a buffer solution containing HA and A-, the H+
consumes A- to form HA. So, [HA] increases while [A-] decreases. When strong
base is added to the buffer, HA is consumed by the added OH- to form A-. Here,
[HA] decreases while [A-] increases. Two steps are required to calculate the
resulting pH – first, a stoichiometry problem for the neutralization; second, an
equilibrium problem for the new concentrations.
For example, calculate the pH of 1 L of the HLc-Lc- buffer (see above) if 0.001
mol NaOH is added.
Stoichimetry: HLc(aq) + OH-(aq)  Lc-(aq) + H2O
HLc + OH-  Lc- + H2O
Before 0.150 0.001 0.130 ---
rxn
Change -0.001 -0.001 +0.001 ---
After rxn ~0.149 ~0 0.131 ---
Equilibrium: HLc(aq)  H (aq) + Lc (aq)
+ -

HLc(aq)  H+(aq) + Lc-(aq)

0.149 ~0 0.131
-x +x +x
~0.149 x ~0.131
[ A−] [ 0.131 ]
pH = pKa + log = 3.85 + log = 3.85 − 0.056 = 3.79
[ HA ] [ 0.149 ]

PRELAB HOMEWORK (to be filled out in your bound lab notebook before you
perform the experiment)
Title and date
Define: (1) pH, (2) weak acid, (3) weak base, (4) buffer, (5) Henderson-Hasselbach
equation,
Answer:
1. When salts dissolve in water, certain ions may be present. Label each of the
following aqueous ions as an acid, base, or neither. Examples: Na+, neither
(non-acid); NO2-, base
a. K+ b. NH4+ c. C2H3O2- d. Cl- e. Zn(H2O)62+ e. Al(H2O)63+
f. CO3 2-

note: SO42- (there is a stronger acid in solution we use here; so this will be
considered non-base in this lab)
2. Write the chemical equilibrium that describes the acid-base behavior of each of
the following species in aqueous solution. Indicate whether the solution should
be acidic, basic, or neutral.
For example, for NO2-: NO2- + H2O  HNO2 + OH- basic
a. ClO- b. (CH3)3NH+ c. F- d. Zn(H2O)62+
3. If 50.0 mL of 1.00 M formic acid (HCOOH) is mixed with 50.0 mL of a 1.00 M
sodium formate (COOH-) solution, what is the pH of the resulting solution? Could
this solution act as a buffer?
Ka of HCOOH is 1.8× 10-4

89
4. Write the equations showing how a buffer solution containing HF and F- would
react with added acid and with added base (2 reactions). Based on the
products of these two reactions, explain why the pH is held fairly constant when
a small amount of acid or base is added.
5. Calculate the molarity of an acetic acid solution (HC2H3O2 = HAc) prepared by
diluting 5 mL 1M HAc to a final volume of 100 mL.
6. Calculate the molarity of an acetate ion solution (C2H3O2- = Ac-) prepared by
diluting 5 mL 1M NaAc to a final volume of 100 mL.
7. Calculate the molarities of HAc and Ac- in a solution prepared by mixing 5 mL
1M HAc with 5 mL 1M NaAc and diluting to a final volume of 100 mL.
Procedure (Experimental Plan)
Data Tables

PROCEDURE

CAUTION: You are working with acids and bases. Handle them with caution
and clean up spills.

Part 1. Hydrolysis of Salts and Solution pH (proton transfer reactions in water)

1) Boil approximately 250 mL deionized water and allow it to cool to room
temperature (be careful when heating/handling).
2) Determine the approximate pH of two water samples and six 0.1M salt solutions
(by observing the colors of six different indicators; see the figure). Test the
solutions in two batches, four at a time.

3) Place 1 drop of an indicator into a well (see below). Add a small volume (about
1 ‘squirt’ from the pipet) of the solution to be tested. Record the color. Do not
fill each well (about ½ way).

4) In addition to unboiled deionized water and boiled deionized water, the six 0.1
M salt solutions to test are: NaCl, NH4Cl, NaC2H3O2, ZnCl2, KAl(SO4)2, and
Na2CO3. The indicators to use are: methyl orange, methyl red, bromothymol
blue, phenol red, phenolphthalein, and alizarin yellow-R.

5) Use the schematics below as a guide. Rinse the well plate with a small amount
of boiled deionized water and dry it before and after each set of observations.
6) Record your estimate of the pH based on the indicator colors.
7) Wash the well plate thoroughly when finished.

Waste disposal: Neutralize all liquid waste with NaHCO3 and dispose down the
drain with a lot of water unless instructed otherwise by your TA.

Note – your TA may instruct you to split up the procedure for part 1 and share with
another lab pair.
Make sure you record all the required data for both sets of solutions.
Note – your TA may instruct you to start with part 2 and do part 1 after that.
Please follow instructions.

90
Set 1:
Methyl Methyl Bromo- Phenol Phenol- Alizarin
orange red thymol blue red phthalein yellow-R

deionized
H2O

boiled
deionized
H2O

NaCl

NaC2H3O2

Set 2:
Methyl Methyl Bromo- Phenol Phenol- Alizarin
orange red thymol blue red phthalein yellow-R

NH4Cl

ZnCl2

KAl(SO4)2

Na2CO3

Part 2a. pH of Buffer Solutions

1) Obtain about 10 mL 1M acetic acid (HC2H3O2, “HAc”) and about 10 mL 1M
sodium acetate (NaC2H3O2, “NaAc”) solutions in small, labeled beakers.
2) Pipet 5 mL 1M HAc into a labeled 100mL volumetric flask and dilute to the mark
with water.

91
3) Pipet 5 mL 1M NaAc into a labeled 100mL volumetric flask and dilute to the
mark with water.
4) Pipet 5 mL 1M HAc into a labeled 100mL volumetric flask; pipet into the same
flask 5 mL 1M NaAc(aq). Dilute to the mark with water.

5) The above steps should provide you with 100 mL of each of the following:
acetic acid solution (HAc), acetate (NaAc) solution, and acetic acid/acetate
solution (HAc/Ac-). The calculation of each solution’s molarity was performed in
your prelab.

6) Measure the pH of the solutions using a calibrated pH meter (see instructions in

lab). The pH meters are delicate and you need to read the printed instructions
carefully (and follow the TA’s instructions, too).
Compare the measured values to those predicted based on literature values.
7) Save the solutions for part 2b.

Part 2b. Effect of Acid and Base on Buffer pH

9) Pipet 1 mL 1.0 M NaOH into the HAc solution and record the pH. Note – there
is a weak acid present to react with the added OH-. Do you expect a huge jump in
pH here?
10) Pipet 1 mL 1.0 M NaOH into the Ac- solution and record the pH. Note – there is
only a weak base present in the initial solution, so what do you think added OH - will
do to the pH here?
11) Pipet 1 mL 1.0 M NaOH into the HAc/Ac- and record the pH. Note – the original
solution is a buffer, so do you expect the pH change to be relatively large or small
here?
12) Please clean the pH meter and leave the electrode immersed in the pH = 7
buffer (yellow solution).

Waste disposal: Neutralize all liquid waste with NaHCO3 and dispose down the
drain with a lot of water unless instructed otherwise by your TA.
DATA ANALYSIS
Part 1. Hydrolysis of Salts and Solution pH (proton transfer reactions in water)
1) For each liquid or solution tested, write the equilibrium expression for the
hydrolysis reaction that would explain your observations.
2) Calculate the Ka or Kb for each cation or anion that hydrolyzes. Compare your
calculated value to the literature value and give possible explanations for the
deviation (if any).

Species Ka at
25oC
HC2H3O2, acetic acid 1.8× 10-5
Al(H2O)63+, hydrated aluminum 1× 10-5 Literature values:
cation
Zn(H2O)62+, hydrated zinc 1× 10-9
cation
H2CO3, carbonic acid 4.3× 10-7
HCO3-, hydrogen carbonate ion 5.6× 10-11
NH4+, ammonium ion 5.6× 10-10

92
Part 2a. pH of Buffer Solutions
3) Calculate the expected pH of the 0.05M HAc, 0.05M Ac-, and 0.05M HAc/0.05M
Ac-. Compare your measured value to the theoretical value and give possible
explanations for the deviation (if any).

Part 2b. Effect of Acid and Base on Buffer pH

4) Calculate the expected pH of 0.05M HAc, 0.05M Ac-, and 0.05M HAc/0.05M Ac-
after the addition of 1mL 0.1 M NaOH to each. Compare your measured pH
value to the theoretical value and give possible explanations for the deviation
(if any).

REPORTING RESULTS – Complete your lab summary

If a report is required in place of a lab summary
Abstract
Results:
Part 1. Hydrolysis equation for each solution
Ka or Kb of each liquid or solution; %error
Part 2a. measured and expected pH of solutions before OH- addition
Part 2b. measured and expected pH of solutions after OH- addition
Sample Calculations:
Part 1. Ka or Kb of each hydrolyzed species; %error
Part 2a. expected pH of solutions before OH- addition
Part 2b. expected pH of solutions after OH- addition
Discussion/Conclusion
Part 1. Did the pH of the solutions match what might be predicted based on
the cation and anion provided by the salt? How good were your
measured Ka or Kb values?
Part 2a. Did the measured pH match the expected pH?
Part 2b. Did the measured pH match the expected pH? Which solution showed
the greatest change in pH? Which showed the least? Why?
Review Questions

REVIEW QUESTIONS
1. Indicate whether the following could act as buffers:
a. 100 mL 0.01 M HNO2 mixed with 100 mL 0.02 M NaNO2.
b. 100 mL 0.01 M HNO2.
c. 100 mL 0.01 M HNO2 mixed with 25 mL 0.02 M NaOH.
2. The Ka of lactic acid, HC3H5O3, is 1.4× 10-4. Over what pH range would a buffer
prepared using equal volumes of 0.1M HC3H5O3 and 0.1M C3H5O3- be most
effective?
3. Find the pH of a 2 10 -5 M HCl solution. If 1 mL of 0.1 M NaOH is added to 1 L of
the acid, what is the resulting pH? How do these pH values compare to the
buffer you made in part 2b?

93
94