Experiment

Hydrolysis of Salts and

pH of Buffer Solutions
To learn about the concept of hydrolysis and to gain familiarity with acid- OBJECTIVE
base indicators and the behavior of buffer solutions.

Apparatus APPARATUS
500-mL Erlenmeyer flask pH meter
150-mL beakers (2) balance AND CHEMICALS
10- and 100-mL graduated cylinders 1-mL pipet
test tubes (6) Bunsen burner and hose
test-tube rack ring stand and iron ring
wire gauze plastic wash bottle
stirring rods (2)

Chemicals
NaC2H302 · 3H20 dropper bottles of:
0.1 M ZnCl2 methyl orange
0.1 M NH4Cl methyl red
0.1 M KAl(S04)z bromothymol blue
0.1 M Na2C03 phenolphthalein
0.1 M NaCl alizarin yellow-R
0.1 M NaC2H302 phenol red
6.0MHCl standard buffer solution (pH 4.5)
3.0 M HC2H302
6.0MNaOH

We expect solutions of substances such as HCl and HN0 2 to be acidic and DISCUSSION
solutions of NaOH and NH 3 to be basic. However, we may be somewhat
surprised at first to discover that aqueous solutions of some salts such as
sodium nitrite, NaN0 2, and potassium acetate, KC 2H302, are basic, where-
as others such as NH 4Cl and FeC1 3 are acidic. Recall that salts are the prod-
ucts formed in neutralization reactions of acids and bases. For example,
when NaOH and HN0 2 (nitrous acid) react, the salt NaN0 2 is formed:

Nearly all salts are strong electrolytes and exist as ions in aqueous solu-
tions. Many ions react with water to produce acidic or basic solutions. The
reactions of ions with water are frequently called hydrolysis reactions. We will
see that anions such as CN- and C2H 30 2- that are the conjugate bases of the
weak acids HCN and HC 2H 30 2, respectively, react with water to form OH-
ions. Cations such as NH 4+and Fe 3+ come from weak bases and react with
water to form H+ ions.

From Laboratory Experiments, Tenth Edition, John H. Nelson and Kenneth C. Kemp. Copyright
© 2006 by Pearson Education, Inc. Published by Prentice Hall, Inc. All rights reserved.

35
Hydrolysis of Salts and pH of Buffer Solutions

Hydrolysis of Anions: Basic Salts

Let us consider the behavior of anions first. Anions of weak acids react with
proton sources. When placed in water these anions react to some extent
with water to accept protons and generate OH- ions and thus cause the so-
lution pH to be greater than 7. Recall that proton acceptors are Brnnsted-
Lowry bases. Thus, the anions of weak acids are basic in two senses: They
are proton acceptors, and their aqueous solutions have pH's above 7. The
nitrite ion, for example, reacts with water to increase the concentration of
OH-ions:

This reaction of the nitrite ion is similar to that of weak bases such as NH 3
with water:

Thus, both NH 3 and N02 - are bases and as such have a basicity or base-
dissociation constant, Kb, associated with their corresponding equilibria.
According to the Brnnsted-Lowry theory, the nitrite ion is the conjugate
base of nitrous acid. Let's consider the conjugate acid-base pair HN0 2 and
N0 2- and their behavior in water:
[H+][N02]
Ka= [HN02]
[HN02J[OH-]
Kb=------
[N02-J

Multiplication of these dissociation constants yields:

K, x K,, = eH=)(~ff]) = [tt+][Off] =Kw

where Kw is the ion-product constant of water.

Thus, the product of the acid-dissociation constant for an acid and the
base-dissociation constant for its conjugate base is the ion-product constant
for water:
[1]
Knowing the Ka for a weak acid, we can easily find the Kb for the anion of the
acid:
Kw
Kb=- [2]
Ka
By consulting a table of acid-dissociation constants, we can find that Ka
for nitrous acid is 4.5 x 10-4• Using this value, we can readily determine Kb
for N02-:

K = 1.0 x 10-14 = 2.2 x 10-11

b 4.5 x 10-4
We note that the stronger the acid is, the larger its Ka, and the weaker its con-
jugate base, the smaller its Kb· Likewise, the weaker the acid (the smaller the
Ka), the stronger the conjugate base (the larger the Kb)·

36
 Hydrolysis of Salts and pH of Buffer Solutions

Anions derived from strong acids, such as Cl- from HCl, do not react with
water to affect the pH. Nor do Br-, r-, N03 -, S04 2-, and Cl0 4- affect the
pH, for the same reason. They are spectator ions in the acid-base sense and
can be described as neutral ions. Similarly, cations from strong bases, such as
Na+ from NaOH or K+ from KOH, do not react with water to affect the pH.
Hydrolysis of an ion occurs only when it can form a molecule or ion that is a
weak electrolyte in the reaction with water. Strong acids and bases do not
exist as molecules in dilute water solutions.

EXAMPLE 1
What is the pH of a 0.10 M NaClO solution if Ka for HClO is 3.0 x 10-8?

SOLUTION: The salt NaClO exists as Na+ and ClO-. The Na+ ions are spectator
ions, but Clo- ions undergo hydrolysis to form the weak acid HClO. Let x equal
the equilibrium concentration of HClO (and OH-):
ClO-(aq) + H10(l) ~ HClO(aq) + OW(aq)
(0.10 - x) M xM xM
The value of Kb for the reaction is (1.0 x 10- )/(3.0 x 10-8) = 3.3 x 10-7 .
14

Because Kb is so small, we can neglect x in comparison with 0.10 and thus

0.10 - x '.::= 0.10.
[HClOJ[OWJ
[ClO-] =Kb
2
_x_ = 3.3 x 10-7
0.10
x 2 = 3.3 x 10-8
x = 1.8 x 10-4 M
pOH = 3.74
and pH = 14 - 3.74 = 10.26
Anions with ionizable protons such as HC0 3- , H 2P04- , and HP042-
may be either acidic or basic, depending on the relative values of Ka and Kb
for the ion. We will not consider such ions in this experiment.

Hydrolysis of Cations: Acidic Salts

Cations that are derived from weak bases react with water to increase the hy-
drogen-ion concentration; they form acidic solutions. The ammonium ion is
derived from the weak base NH 3 and reacts with water as follows:

This reaction is completely analogous to the dissociation of any other weak

acid, such as acetic acid or nitrous acid. We can represent this acid-dissociation
of NH 4 + more simply:

Here too the acid-dissociation constant is related to the Kb of NH 3, which is

the conjugate base of NH4 +:

37
 Hydrolysis of Salts and pH of Buffer Solutions

Knowing the value of Kb for NH 3, we can readily calculate the acid dissocia-
tion constant from Equation [3]:
Kw
Ka= Kb [3]

Cations of ~~-~1)5ali metals (Group lA) and the larger ap~~l_i!le earth ions,
_C:::a 2+, Sr 2 \~n_tj_}!~+, do not reacthwHh water, because they come from strong
bases. Thus, these ions have no influence on the pH of aqueous solutions.
They are merely spectator ions in acid-base reactions. Consequently, they are
described as being neutral in the acid-base sense. The cations of most other
metals do hydrolyze to produce acidic solutions. Metal cations are coordi-

)I nated with w~ter molecules, and it is the hydrated1on th~t)?~IY~.s ~-s t_h~p_!"o­
~The following equa tionsillustrate"thls "behavior for the hexaaqua
iron (III) ion:

We frequently omit the coordinated water molecules from such equations.

For example, Equation [4] may be written as
[5]

Additional hydrolysis reactions can occur to form Fe(OH)z +and even lead to
the precipitation of Fe(OHh. The eguilibria for such cations are _Qg_~~O_f!!.:
plex, and not all specie~ have been identified. However, equations such as [4]
and [5] serve to illustrate the acidic character of dipositive and tripositive
ions and account for most of the H+ in these solutions.

Summary of Hydrolysis Behavior

Whether a solution of a salt will be acidic, neutral, or basic can be predicted
on the basis of the strengths of the acid and base from which the salt was
formed.

vJ-vJ,,... c..
r J 1. Salt of a strong acid and a strong base: Examples: NaCl, KBr, and
Ba(N03)z. Neither the cation nor anion hydrolyzes, and the solution
has a pH of 7.
./ 2. Salt of a strong acid and a weak base: Examples: NH 4 Br, ZnC1 2 , and
Al(N0 3)3. The cation hydrolyzes, forming H+ ions, and the solution
has a pH less than 7.
3. Salt of a weak acid and a strong base: Examples: NaN0 2 , KC 2H30 2 , and
Ca(OCl)z. The anion hydrolyzes, forming OH- ions, and the solution
has a pH greater than 7.
4. Salt of a weak acid and a weak base: Examples: NH 4 F, NH 4C2H 30 2 , and
Zn(N0 2)z. Both ions hydrolyze. The pH of the solution is determined
by the relative extent to which each ion hydrolyzes.

In this experiment, we will_!~?Ltb-~L.Et!.._of water and of sever~l aqueous

salt solutions to determTrie-whether these solutions are acidfr, basic, or
neutral.In each case~"ih:e-saffsoTutio~.-""'JJLl?.g___ Q_.J . !vf. Knowing the concen-
tration of the salt solution and the measured pH of each solution allows us
to calculate Ka or Kb for the ion that hydrolyzes. Example 2 illustrates such
calculations.

38
 Hydrolysis of Salts and pH of Buffer Solutions

EXAMPLE 2
Calculate Kb for OBr- if a 0.10 M solution of NaOBr has a pH of 10.85.

SOLUTION: The spectator ion is Na+. Alkali metal ions do not react with water
and have no influence on pH. The ion OBr- is the anion of a weak acid and thus
reacts with water to produce OH- ions:

and the corresponding expression for the base dissociation constant is

[HOBr][OW]
Kb= [OBr-] [6]
If the pH is 10.85, then

pOH = 14.00 - 10.85 = 3.15

and

[OH-] = antilog (-3.15) = 7.1 x 10-4 M

The concentration of HOBr that is formed along with OH- must also be
7.1 x 10-4 M. The concentration of OBr- that has not hydrolyzed is

[OBr-] = 0.10 M - 0.00071 M ~ 0.10 M

Substituting these values into Equation [6] for K1i yields

[7.1 x 10-4 ][7.1 x 10-41

Kb= [0.10]
= 5.0 x 10-6
We will use a set of indicators to determine the pH of various salt solu-
_!lgns. The dark areas in Figure 1 denote the transition ranges for the indica-
tors you will use.
We will _g~_!}:i'.l~~~:.L!h~Uh~ . ~2~-1:!!!9.12.S ~~~~-~e ~~s~ ~~~}. _b,e __I?ore (l~i~ic
_!!_1a~~~~o~l? E!~~~_<::t_!l1e.m t<?_E~ A major reason for this increased acidity
is the occurrence of C0 2 dissolved in the solutions. C0 2 reacts with water to flJ__;]
generate H+:
(".f ~- c ~ t;C.// A-·
c .'J;u f . --o~~-
The solubility of C0 2 is greatest in basic solutions, intermediate in neutral (2.,,' r-
ones, and least in acidic ones. Even distilled water will therefore be some-
what acidic, unless it is boiled to remove the dissolved C02.
/-- i..C-< '-·0 lp /~ ~ /-e_; c-
Buffer Solutions .t;, o(p j
Chemists, biologists, and environmental scientists frequently need to control
the pH of aqueous solutions. The effects on pH caused by the addition of a
small amount of a strong acid or base to water are dramatic. The addition of
a mereQ_'.90l~ole ofHCl to 1 L of water causes the pH to drop instantly from
7'.0 to 3.0 ~~jtie_Jjyqroniurn:-jQµ_<:9J:1Centration increases from 1 x 10-7 to
l -x 10-'--~ mol/L. And, on the other hand, the addition of 0.001 mole of NaOH

39
 Hydrolysis of Salts and pH of Buffer Solutions

13
Red
12.0
12
A~
yeJ.loW.;.~
11
Red
10.0
10
Red ~~~1- 10.l
phthalein
9
Blue
8.0
8
7.6 ·Phenol 8.2
Yellow
:. red· Colorless
7
Yellow Bn»nofhymol 6.6
6.0 blue
6
Yellow Methyl 6.0 Yellow
red
5
4.4 4.8
Yellow
4
Methyl Red
orange
3
3.1
Red
2
Color changes

• FI GU RE l The color behavior of indicators.

to 1 L of water will cause the pH to increase from 7.0 to 11.0. That life could
not exist without some mechanism for controlling or absorbing excess acid
or base is indicated by the narrow normal range of blood pH, 7.35 to 7.45.
The control of pH is often accomplished by use of buffer solutions (often
simply called buffers). A buffer solution has the important property of resist-
ing large changes in pH upon the addition of small amounts of strong acids
or bases. A buffer solution must have two components-one that will react
with H+, and the other that will react with OH-. The two components of a
buffer solution are usually a weak acid and its conjugate base, such as
HC2H302-C2H302- or NH4 +-NH3. Thus, buffers are often prepared by mix-
ing a weak acid or a weak base with a salt of that acid or base. For example,
the HC 2H30rC 2H 30 2-buffer can be prepared by adding NaC2H302 to a so-
lution of HC 2H30 2; the NH 4+-NH3 buffer can be prepared by adding
NH 4Cl to a solution of NH 3. By the appropriate choice of components and
their concentrations, buffer solutions of virtually any pH can be made.
Let's examine how a buffer works. Consider a buffer composed of a hypo-
thetical weak acid HX and one of its salts MX, where M+ could be Na+, K+,
or other cations. The acid-dissociation equilibrium in this buffer involves
both the acid, HX, and its conjugate base x-:

[1]

The corresponding acid-dissociation-constant expression is

[2]

40
 Hydrolysis of Salts and pH of Buffer Solutions

Solving this expression for [H+], we have

+ [HXl
[H ] = Ka [X-] [3]

We see from this expression that the hydrogen-ion concentration and there-
fore the pH is determined by two factors: the value of Ka for the weak acid
component of the buffer, and the ratios of the concentrations of the weak
acid and its conjugate base, [HX]/[X-].
If OH- ions are added to the buffered solution, they react with the acid
component of the buffer:
[4]
This reaction results in a slight decrease in the [HX] and a slight increase in
the [X-], as long as the amounts of HX and x- in the buffer are large com-
pared to the amount of the added OH-. In that case, the ratio [HXl/[X-]
doesn't change much, and thus the change in the pH is small.
If H+ ions are added to the buffered solution, they react with the base
component of the buffer:
H+(aq) + x-(aq) ~ HX(aq) [5]
This reaction causes a slight decrease in the [X-l and a slight increase in the
[HX]. Once again, as long as the change in the ratio [HX]/[X-l is small, the
change in the pH will be small.
Buffers resist changes in pH most effectively when the concentrations of
the conjugate acid-base pair, HX and x-, are about the same. We see from ex-
amining Equation [31 that under these conditions their ratio is close to one,
and thus the [H+] is approximately equal to Ka· For this reason we try to se-
lect a buffer whose acid form has a pKa close to the desired pH.
Because we are interested in pH, let's take the negative logarithm of both
sides of Equation [3] and obtain
[HX]
- log[H+] = - log Ka - log [X-]

Because -log[H+] = pH and -log[ Ka] = pKa, we have

[HX]
pH = pKa - log [X-]

and making use of the properties of logarithms (see Appendix A) we have

[6]

and in general
[conjugate base]
pH = pKa + log [wea k ac1'd] [7]

This relationship is known as the Henderson-Hasselbalch equation. Biochemists,

biologists, and others who frequently work with buffers often use this equa-
tion to calculate the pH of buffers. What makes this equation particularly con-
venient is that we can normally neglect the amounts of the acid and base of
the buffer that ionize. Therefore, we can use the initial concentrations of the
acid and conjugate base components of the buffer directly in Equation [7].

41
Hydrolysis of Salts and pH of Buffer Solutions

EXAMPLE 3
What is the pH of a buffer that is 0.120 Min lactic acid, HC 3H 50 3, and 0.100 M
in sodium lactate, NaC 3H 50 3? For lactic acid, K11 = 1.4 X 10-4 .

SOLUTION: Because lactic acid is a weak acid, we will assume that its initial
concentration is 0.120 Mand that none of it has dissociated. We will also assume
that the lactate ion concentration is that of the salt, sodium lactate, 0.100 M. Let x
represent the concentration in mol/L of the lactic acid that dissociate. The initial
and equilibrium concentrations involved in this equilibrium are

Initial 0.120 M 0 O.lOOM

Change -xM +xM +xM

Equilibrium (0.120 - x) M xM (0.100 + x) M

The equilibrium concentrations are governed by the equilibrium expression

Because Ka is small and the presence of a common ion, we expect x to be small

relative to 0.12 and 0.10 M. Thus, our equation can be simplified to give

_
4
x(0.100)
1.4 x 10 = 0.120

Solving for x gives a value that justifies our neglecting it:

2
x = [H+] = (0.1 0)(l.4 x 10-4 ) = 1.7 x 10-4 M
0.100

pH = -log(l.7 x 10-4) = 3.77

Alternatively, we could have used the Henderson-Hasselbalch equation to calcu-

late the pH directly:

[conjugate base]) (0.100)

pH= pKa +log ( [weak acid] = 3'85 +log 0.120

= 3.85 + ( -0.08) = 3.77

Addition of Strong Acids or Bases to Buffers

Let's consider in a quantitative way the manner in which a buffer solution
responds to the addition of a strong acid or base. Consider a buffer that con-
sists of the weak acid HX and its conjugate base x- (from the salt NaX).
When a strong acid is added to this buffer, the H+ is consumed by the x- to
produce HX; thus [HX] increases and [X-] decreases. Whereas, when a
strong base is added to the buffer, the OH- is consumed by HX to produce
x-; in this case, [HX] decreases and [X-] increases. There are basically two

42
 Hydrolysis of Salts and pH of Buffer Solutions

steps involved in calculating how the pH of the buffer responds to the addi-
tion of a strong acid or base. First consider the acid-base neutralization reac-
tion and determine its effect on [HX] and [X-]. And second, after performing
this stoichiometric calculation, use Ka and the new concentrations of [HX]
and [X-] to calculate the [H+]. This second step in the calculation is a stan-
dard equilibrium calculation. This procedure is illustrated in Example 4.

EXAMPLE 4
A buffer is made by adding 0.120 mol HC 3H 50 3 and 0.100 mol NaC 3H 50 3 to
enough water to make 1.00 liter of solution The pH of the buffer is 3.77 (see
Example 3). Calculate the pH of the solution after 0.001 mol NaOH is added.

SOLUTION: Solving this problem involves two steps.

Stoichiometric calculation: The OH- provided by the NaOH reacts with the
HC 3Hs0 3, the weak-acid component of the buffer. The following table summa-
rizes the concentrations before and after the neutralization reaction:

Before reaction 0.120M 0.001 M - 0.lOOM

Change -0.001 M -0.001 M - +0.001 M
After reaction 0.119 M O.OM - 0.101 M

Equilibrium calculation: After neutralization the solution contains different

concentrations for the weak acid-conjugate base pair. We next consider the pro-
ton-transfer equilibrium in order to determine the pH of the solution:

Before reaction 0.119 M - 0 0.101 M

Change -xM - +xM +xM
After reaction (0.119 - x) M - xM (0.101 + x) M

[H30+][C3H503 -] (x)(0.101 + x) (x)(0.101) _4

Ka = . = ::::::: = 1.4 x 10
[HC 3Hs0 3] 0.119 - x 0.119

+ (0.119)(1.4 x 10-4) -4
x = [H30 J = (O.lOl) = 1.65 x 10 M

pH = -log(l.65 x 10-4 ) = 3.78

Note how the buffer resists a change in its pH. The addition of 0.001 mol of
NaOH to a liter of this buffer results in a change in the pH of only 0.01 units,
whereas the addition of the same amount of NaOH to a liter of water results in a
change of pH from 7.0 to 11.0, a change of 4.0 pH units!

A. Hydrolysis of Salts
Boil approximately 450 mL of distilled water for about 10 min to expel dis- PROCEDURE
solved carbon dioxide. Allow the water to cool to room temperature. While

43
 Hydrolysis of Salts and pH of Buffer Solutions

the water is boiling and subsequently cooling, add about 5 mL of unboiled

distilled water to each of six test tubes. Add three drops of a different indica-
tor to each of these six test tubes (one indicator per tube) and record the col-
ors on the report sheet. From these colors and the data given in Figure 1,
determine the pH of the un~oi~~--~at~E-~~-~h~ n~~~~t E!! ~!1.!~· (Remember
that we would expect its pH to be below 7 because of dlssofved C0 2.) Empty
the contents of the test tubes and rinse the test tubes three times with about 3
mL of boiled distilled water. Then pour about 5 mL of the boiled distilled
water into each of the six test tubes and add three drops of each of the indi-
cators (one indicator per tube) to each tube. Record the colors and determine
the pH. Empty the contents of the test tubes and rinse each tube three times
with about 3 mL of boiled distilled water.
Repeat the same procedure to determine the pH of each of the following
solutions that are _QJ__ l\:1:_ NC\~L NaC:. 2H3Qi.t..NtIAcC:::L ZnCl2, KAl(S0 4 h, and
Na 2C0 3. Use 5 mL of each of these solutions per test tube. Do not forget to
rinse the test tubes with boiled distilled water when you go from one solu-
tion to the next.
From the pH values that you determined, calculate the hydrogen- and hy-
droxide-ion concentrations for each solution. Complete the tables on the re-
port sheets and calculate the Ka or Kb as appropriate.
Dispose of chemicals in designated receptacles.

B. pH of Buffer Solutions
1. Preparation of Acetic Add-Sodium Acetate Buffer
Weigh abou!_~?-.S.c:>~Na~z!:IJ92...'.}J:! 2_Q_ to the nearest 0.01 g, record its mass,
and add it to a 150-mL beaker. Using a 10-mL graduated cylinder, measure
8.8 mL of_3_.Q_~L~f~.tic~sj_d and add it to the beaker containing the sodium ac-
etate. Using a graduated cylinder, measure 55.6 mL of distilled water and
add it to the solution of acetic acid and sodium acetate. Stir the solution until
all of the sodium acetate is dissolved. The pH of this solution will be mea-
~~!f:'_~--~~~:1:1:g a B.!i-=-~· The operation and calibration o(thepR.meter are
described in the next section. Calibrate the pH meter using a standard buffer
with a pH of 4.5. After you have calibrated the pH meter, measure the pH of
the buffer solution you have prepared and record the value. Save this buffer
solution for part 2 below.

Operation and Calibration of the pH Meter

1. Obtain a buffer solution of known pH.
2. Plug in the pH meter to the line current and allow at least 10 min for
warming up. It should be left plugged in until you are completely fin-
ished with it. This does not apply to battery-operated meters.
3. Turn the function knob on the pH meter to the standby position.
4. Prepare the electrodes. Make certain that the solution in the reference
electrode extends weITa&ove-the· internal electrode. If it does not, ask
( /' r. I
your mstructor to fffCit with-s~tur-ated KCl soiutio-n.
Remove the rub-
~ e,I
I

I '.Ju~· ber tip and slide down the rubber collar on the reference electrode.
Rinse the outside of the electrodes well with distilled water.
5. Standardize the pH meter. Carefully immerse the electrodes in the buffer
solution contained in a small beaker. Remember that the glass electrode is
~~eaks eas_j]y! Do not touch the bottom of the beaker with
the electrodes!! Turn the function knob to "read" or "pH." Turn the

44
 Hydrolysis of Salts and pH of Buffer Solutions

standardize knob until the pH meter indicates the exact pH of the

buffer solution. Wait 5 s to be certain that the reading remains constant.
Once you have sta':!g_E~c.ij_~ed _!!!_~_p_Ij__~e_!_e~~ dq__ ':l..~!.!!.!!.'!l1:!.5.~_t.h!!__~~q!.!_q3_!.qize
k1:!_qb. Turn the function knob to stanaDy. Carefully lift the electrodes
-·from the buffer and rinse them with distilled water. The pH meter is
now ready to use to measure pH.

2. Effect of Acid and Base on the Buffer pH

Pour_ half .9-~- mL) of the buffer solution you prepared above into another
150-mL-beaker. Label the two beakers 1 and 2. (CAUTION: Concentrated
HCL can cause severe burns. Avoid contact with it. If you come--fiicontad
with it, immediately wash the area with copious amounts of water.) Pi pet
1.0 mL of 6.0 M }f Cl into beaker 1, mix, and then measure the pH of the re-
Sllitint soiution and.- record
the pH. Remember to rinse the electrodes be-
tween pH measurements. (CAUTION: Sodium hydroxide can cause severe
burns. Avoid contact with it. If you come in contact with it, immediately
wash the area with copious amounts of water.) Similarly, £!£~!.LO ~L of
6.0 M NaOH into beaker 2, mix, and then measure and record the pH ofthe
resultant solution. Calculate the pH values of the original buffer solution,
the values after the additions of the HCl and NaOH. How do the measured
and calculated values compare? Dispose of the chemicals in the designated
receptacles.

Before beginning this experiment in the laboratory, you should be able to an- PRE LAB
swer the following questions: QUESTIONS
1. Define Bmnsted-Lowry acids and bases.
2. Which of the following ions will react with water in a hydrolysis reac-
tion: Na+, Ca 2+, Cu 2+, Zn2+, F-, SO/-, Br-?
3. For those ions in question 2 that undergo hydrolysis, write net ionic
equations for the hydrolysis reaction.
4. The Ka for HCN is 4.9 x 10-10• What is the value of Kb for CN-?
5. What are the conjugate base and conjugate acid of H 2P0 4-?
6. From what acid and what base were the following salts made:
CaS04, NH4Br, and BaCl2?
7. Define the term salt.
8. Tell whether 0.1 M solutions of the following salts would be acidic,
neutral, or basic: BaC1 2, CuS0 4, (NH 4)zS04, ZnC1 2, NaCN.
9. If the pH of a solution is 8, what are the hydrogen- and hydroxide-ion
concentrations?
10. The pH of a 0.1 M MCI (M+ is an unknown cation) was found to be 4.7.
Write a net ionic equation for the hydrolysis of M+ and its correspond-
ing equilibrium expression Kb. Calculate the value of Kb·
11. What is the pH of a solution that is 0.10 M HC 2H 30 2 and 0.20 M
NaC2H302? Ka for acetic acid 1.8 X 10-5.

45
NOTES AND CALCULATIONS

46
Name _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ Desk _ _ _ _ _ _ _ _ _ __

D a t e - - - - - - - - - - Laboratory Instructor - - - - - - - - - - - - - - -

REPORT SHEET EXPERIMENT

Hydrolysis of Salts
and pH of Buffer Solutions
A. Hydrolysis of Salts

Ion expected to Spectator ion(s)

Solution hydrolyze (if any) (if any)

0.1 MNaCl

0.1 M ZnC1 2

0.1 M KAI(S04h

47
 Indicator Color*
Bromo- Phenol-
Methyl Methyl thymol Phenol phtha- Alizarin
Solution orange red blue red le in yellow-R pH

H 20 (unboiled)

H 20 (boiled)

NaCl

·color key: org = orange; - = colorless; yell = yellow.

CALCULATIONS

Net-ionic equation for Expression for equilibrium

Solution hydrolysis constant (Ka or Kb) Value of Ka or Kb

ZnCl2
 Report Sheet • Hydrolysis of Salts and pH of Buffer Solutions

QUESTIONS
1. Usinf the Ka's for HC 2H 30 2 and HC0 3 - (from Appendix E), calculate the Kb's for the C 2H 30 2- and
C0 3 - ions. Compare these values with those calculated from your measured pH's.

2. Using Kb for NH 3 (from Appendix F), calculate Ka for the NH 4 +ion. Compare this value with that calcu-
lated from your measured pH's.

3. How should the pH of a 0.1 M solution of NaC 2H 30 2 compare with that of a 0.1 M solution of KC 2H 30 2 ?
Explain briefly.

4. What is the greatest source of error in this experiment? How could you minimize this source of error?

B. pH of Buffer Solutions
Mass of NaC 2H30 2 • 3H 20 (FW = 136 g/mol)
pH of Original buffer solution - - - - - - - - - - - - -
pH ofBuffer + HCl - - - - - - - - - - - - - - - -
pH Buffer + NaOH - - - - - - - - - - - - - - - -
Calculate pH of original buffer. (Show calculations below.) _ _ _ _ __

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 Report Sheet • Hydrolysis of Salts and pH of Buffer Solutions

Calculate pH of buffer + HCl. (Show calculations below.) ~----

Calculate pH of buffer+ NaOH. (Show calculations below.) _ _ _ _ __

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NOTES AND CALCULATIONS

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 Answers to Selected
Pre Lab Questions
1. According to the Bronsted-Lowry definitions, an acid is a proton donor
and a base is a proton acceptor.
2. Cuz+, Zn2+, and S03 2- will undergo hydrolysis.
3. For example, Cuz+(aq) + 2H 20(Z) Cu(OH)i(s) + 2H+(aq).
4. Kb = 1.0 x 10-14/4.9 x 10-10 = 2.0 x 10-5
5. The conjugate base is HP042- and the conjugate acid is H 3P04.
6. For example, CaS04 may be made from Ca(OHh and H 2S04.
11. pK11 = -log(l.8 x 10-5) = 4.74 and pH = 4.74 + log(0.20/0.10) =
4.74 + (0.30) = 5.04

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