Experiment 3

Title: Hydrolysis of Salts and choice of Indicators / Titration Curve

Objectives:

1. To determine the degree of hydrolysis of NH4+

2. To find out the suitable indicator that needed for acid-base titration
3. To find out the pH value of Sodium salts
4. To determine the hydrolysis of salts
5. To study the relationship between strength of an acid and the strength of its
conjugate base
6. To determine the pH of ammonium chloride, sodium acetate, sodium formate,
sodium carbonate, and distilled water
7. To carry out titration between sodium hydroxide, hydrochloric acid, and also
ethanoic acid in order to find out the suitable indicator for each titration

Introduction:

There are many different types of salts can be found to exists in nature. The sea
contains many salts such as sodium chloride, potassium chloride, magnesium chloride,
magnesium sulphate and potassium bromide. Besides, the earth crust is made up of
minerals containing various types of salts such as sodium fluoride, magnesium sulphate, lead
(II)Sulphide and also calcium carbonate. A salt is an ionic compound consisting of a cation
such as metal ion or an ammonium ion from a base and an anion from an acid. Thus, in
another word, salt is a compound formed when the hydrogen ion in an acid is replaced by a
matal ion or an ammonium ion. Salt also can be formed in a neutralization reaction between
an acid and a base.

Acid + Base Salt + Water

HCL(aq) + NaOH (aq) NaCl (aq) + H20(l)

They are composed of cations (positively charged ions) and anions (negative ions) so that the
product is electrically neutral (without a net charge). These component ions can be inorganic
such as chloride (Cl−), as well as organic such as acetate (CH 3COO−) and monatomic ions such
as fluoride (F−), as well as polyatomic ions such as sulfate (SO 42−). There are several varieties
of salts. Salts that hydrolyse to produce hydroxide ions when dissolved in water are basic
salts and salts that hydrolyse to produce hydronium ions in water are acid salts. Neutral salts
are those that are neither acid nor basic salts. Zwitterions contain an anionic centre and a
cationic centre in the same molecule but are not considered to be salts. Examples included
amino acids, many metabolites, peptides and proteins.

Salts can appear to be clear and transparent (sodium chloride), opaque, and even
metallic and lustrous (iron disulfide). In many cases the apparent opacity or transparency are
only related to the difference in size of the individual monocrystals. Since light reflects from
the grain boundaries (boundaries between crystallites), larger crystals tend to be
transparent, while polycrystalline aggregates look like white powders. Of course, some salts
are opaque.

Salts are strong electrolytes which may be prepared by evaporating to dryness a

solution containing equivalent amounts of an appropriate acid and base. This is concerned
with the reactions of these salts with water, for instance, the hydrolysis of salts. In
additional, salts are ionic compounds and they can dissolve in water. When a salt dissolved
in water, the crystalline lattice structure is destroyed and the solution may be regarded as
containing a large number of positive and negative ions. Depending on the relative strength
of these ions as acids or bases, they can either capture protons from water, or donate
protons to water, and thus determining the pH of the solutions.

Acid-base reactions are essential in both biochemistry and industrial chemistry.

According to Arrhenius definition, an acid is a substance like HCL that dissolve in water to
produce H+ ions (protons) and a base is a substance like NaOH that dissolves in water to
produce hydroxide (OH-) ions.

HCL(g) H2O(l) H+(aq) + Cl-

NaOH(s) H2O(l) Na+(aq) + OH-

Acid differs in the number of hydrogen ions they can donate. For instance, monoprotic acids
are compound that are capable of donating a single proton per molecule. Monoprotic acids
include HF, HCL, HBr, HI, HNO3 and HNO2. All carboxylic acids that contain a single –COOH
group, such as acetic acid (CH3COOH), are monoprotic acids, dissociating to form RCOO- and
H+. However, polyprotic acids can donate more than one hydrogen ion per molecule. For
instance, H2SO4 can donate two hydrogen ions and also diprotic acid H3PO4 capable
donating three protons in successive steps.

H3PO4 (l) H20(l) H+(aq) + H2PO4-(aq)

H2PO4 – (aq) H+(aq) + HPO4 2- (aq)

HPO4 2-(aq) H+(aq) + PO4 3- (aq)

A double arrow is used to indicate that both the forward and reverse reactions occur
simultaneously, so forward reaction does not go to completion. Instead, the solution
contains significant amounts of both reactants and products. Over time, the reaction reaches
a state in which the concentration of each species in solution remains constant. The reaction
then said to be in equilibrium.

We can state that strong acids react essentially completely with water to give H+
and the corresponding anion. Similarly, strong bases dissociate essentially to completely in
water to give OH- and corresponding cation. Thus, strong acids and strong bases are both
strong electrolytes. In contrast, only fraction of the molecules of weak acids and weak bases
react with water to produce ions, so weak acids and weak bases are weak electrolytes.
Almost less than 5 %of weak electrolytes dissociates into ions in solution, whereas more
than 95 % is present in un-dissociated form. Common strong acids are HCL, HBr, HI, HNO3,
HCIO4, and H2SO4. While the most common strong bases are ionic compounds that contain
the hydroxide ion as the anion such as NaOH, KOH, and Ca(OH)2. However, common weak
acids include HCN, H2S, HF and etc.

Apparatus:

1. Conical Flask (s)

2. Measuring Cylinder (s)
3. Retort stand
4. White Tile
5. Electronic pH meter
6. Burette
7. Pipette
8. 50 ml Beaker(s)

Chemicals:

1. Bromophenol blue indicator

2. Phenolphthalein indicator
3. HCL
4. HOAc, ethanoic acid
5. 1mol/dm3 ammonium chloride
6. 1mol/dm3 sodium acetate
7. 1mol/dm3 sodium formate
8. 0.5 mol/dm3 sodium carbonate
9. Sodium Hydroxide, NaOH

Procedures:

1. The apparatus was set up as shown in diagram 3.1.

2. 10 ml of 1 mol/dm3 NH4Cl was pipetted into a 50 ml beaker by using a pipette.

Then the pH of 1 mol/dm3 of NH4Cl solution was measured by using an
electronic pH meter.
3. Then, 10 ml of 1 mol/dm3 Sodium acetate CH3COONa, Sodium formate
HCOONa, and also 10ml of 0.5 mol/dm3 Sodium Carbonate Na2CO3 solutions
were separately pipetted into 3 different 50 ml beakers by using pipette. The pH
of each solution was measured by using an electronic pH meter.

4. The HCl and HOAc in conical flask were titrated with Sodium Hydroxide, NaOH
by setting up burette with retort stand. Few drops of Bromophenol blue
indicator was added into the solution of conical flask in order to determine the
volume of NaOH used by observing the yellow colour of indicator change into
blue colour. This method was repeated twice to get an average volume reading
of NaOH used in titration.
 5. The method 4 was repeated by using Phenolphthalein Indicator and the average
volume reading of NaOH used in titration was recorded. The colour of indicator
change from colourless to pink was noted in order to determine the total
volume of NaOH used.

Results:

Table 1: The pH value of different salt solutions

Salts Solution pH Value

1. Ammonium Chloride, NH4Cl 5.20
2. Sodium Acetate, CH3COONa 8.15
3. Sodium Formate, HCOONa 7.27
4. Sodium Carbonate, Na2CO3 11.23
pH value of H2O : 7.24

Table 2:

Reading(s) Bromophenol Blue Indicator Phenolphthalein Indicator

Initial volume / cm3 of HCl HOAc HCl HOAc
NaOH used 0.70 17.40 0.00 2.50 8.45 25.90 34.50 24.50
Final volume/ cm3 of 8.95 25.90 2.50 4.90 17.40 34.50 44.50 34.50
NaOH used
Volume/ cm3 of NaOH 8.25 8.50 2.50 2.40 8.95 8.60 10.00 10.00
used
Average volume/ cm3 of 8.375 2.45 8.525 10.00
NaOH used
Questions:

Part A: Ammonium Chloride

1. Do you expect an ammonium chloride solution to be neutral?

Answer: No

2. On what previously obtained EXPERIMENTAL evidence do you base your above

answer?
Answer:
Ammonium chloride solution is not expected to be neutral, but acidic. From the data
given, it has a pH value of 5.20. Ammonium chloride is the salt resulted from the
reaction between strong acid and weak base. The dissociation of ammonium
chloride in water will produce hydroxonium ions (H3O+).

3. Measure the pH of a 1 mol/dm3 solution of ammonium chloride.

Answer: pH = 5.20

4. Is the solution more acidic or basic than pure water?

Answer: It is more acidic than pure water.

5. Write an equation for the reaction causing this.

Answer: NH4+(aq) + H20 (l) NH3(aq) + H3O+(aq)

6. Bronsted defined an acid as a proton donor and a base as a proton acceptor. What is
water in this reaction?
Answer: Since NH4Cl is an acid substance which act as a proton donor, the water
which reacts with NH4Cl will receive the proton from it, thus water is a base which
accept the proton from NH4Cl.

7. Write an expression for the hydrolysis constant Ka (NH4+)

Answer: Ka(NH4+) = [NH3][H3O+]/ [NH4+]

8. What are concentrations of the following ions in solution?

Answer:
a. [H3O+] = 6.31 x 10^-6 mol/dm^3
b. [NH4+] = 1.0 mol/dm^3
c. [Cl-]= 1.0 mol/dm^3
d. [OH-]= 1.58 x 10^-9 mol/dm^3
e. [NH3]= 6.31 x 10^-6 mol/dm^3
 9. Now calculate Ka(NH4+).
Answer: Ka(NH4+) = [NH3][H3O+]/[NH4+]
= (6.31x10^-6mol/dm^3)(6.31x10^-6mol/dm^3)
(1.0mol/dm^3)
= 3.98x10^-11mol/dm^3

10. What is the degree of hydrolysis of NH4+?

Answer: 6.31 x 10^-6 mol/dm^3

11. Realizing that you have a solution of ammonium chloride at the end point of the
titration of the strong acid hydrochloric acid and weak base ammonia, what
indicator would you use to detect this end point in such a titration of approximately
molar solution?
Answer: Methyl red that has pH range of 3.1 – 4.4 indicator will be used to detect
the end point as the ammonium chloride is the salt produced at the end point of
titration between a strong acid hydrochloric acid and weak base ammonia, which at
the end point, pH < 7.

Part b: Sodium Salts:

1. Measure the pH of 1M sodium acetate, 1 mole dm^-3 sodium formate and 0.5 M
sodium carbonate solutions, and complete the following table.

CH3COONa HCOONa Na2CO3

Sodium Acetate Sodium Formate Sodium Carbonate
pH 8.15 7.27 11.23
[H3O+]/moldm^-3 7.08x10^-9 5.37x10^-8 5.89x10^-12
[OH-]/moldm^-3 1.41x10^-6 1.86x10^-7 1.70x10^-3
[Na+]/moldm^-3 1.00 1.00 1.00

2. What are the concentrations of the following ions in NaAc solution?

a. [CH3COOH] = 1.41x10^-6 moldm^-3
b. [CH3COO-] = (1 – 1.41 x 10-6 ) mol/dm3

3. What is the % of hydrolysis of acetate ion?

Percentage of hydrolysis = degree of hydrolysis x 100%
= 1.41x10^-6 x100%
= 1.41x10^-4%
 4. What indicator would you use for the titration of acetic acid with strong base?
Why?
Answer: Phenolphthalein. It is because titration of acetic acid with strong base has a
range of pH 7 – pH11 as their end point. Therefore, phenolphthalein which has a pH
range of 8 – 10 is suitable to test the end point.

5. Write an equation for the reaction of formate ion with water.

Answer: HCOO- (aq) + H2O HCOOH(aq) + OH- (aq)

6. Considering the second protonation is small, find the concentration of H3O+, OH-,
HCO3-, and CO3 2- in Na2CO3 solution.
Answer:
a)[H3O+] = 5.89x10^-12 mol/dm3
b)[HCO3-] = 1.70x10^-3mol/dm3
c)[OH-] = 1.70x10^-3 mol/dm3
d)[CO3 2-] = 0.4983 mol/dm3

7. Comment on the relative basic strengths of acetate, formate, and carbonate ions.
Answer: The basic strength of carbonate ions is bigger than acetate ions. However,
the basic strength of acetate ions is bigger than formate ions. CO32- > CH3COO- >
HCOO-

8. Does this agree with the fact that formic acid is a stronger acid than acetic acid and
acetic acid is stronger acid than the bicarbonate ion?
Answer: Yes

9. Consequently, what is the relationship between the strength of an acid and the
strength of conjugate base?
Answer: The stronger the acid, the weaker the conjugate base
10. Derive the mathematical form for a general weak acid
H20 + HA H3O+ + A-
from the equation Ka and Kb above.

Part c: Acid-base titration with different indicators

Answer:
For the titration of sodium hydroxide and hydrochloric acid with different indicators,
the results obtained were quite similar with minor difference. This was a strong acid
and strong base titration, before and after the end point was reached, there was a
sharp increase in pH from pH 3 – pH 11. Any indicator that change colour within the
range can be used as the indicator of the titration. Phenolphthalein has pH range of
8 – 10 while Bromophenol blue has pH range of 3.0 – 4.6. Therefore both of the
indicators were suitable for the titration.

For the titration of sodium hydroxide and ethanoic acid with different indicator, the
results obtained were totally different. For weak acid and strong base titration, the
pH range before and after the end point was 7 – 11. Any indicators that change
colour within this range can be used as indicator for this titration. Only
phenolphthalein was suitable in the titration.

The concentration of HCl when bromophenol blue indicator was added is 0.084
mol/dm^3, while the concentration of HCl when phenolphthalein was added is 0.085
mol/dm^3. Thus, this indicate a small change when 1 mole of NaOH reacts with one
mole of HCl, and both indicator are suitable used to determine its end point where
both indicators has pH range of 8 – 10 and 3.0 – 4.6 respectively.

On the other hand, the concentration of HOAc when bromophenol blue indicator
was added is 0.025mol/dm^3, while the concentration of HOAc when
phenolphthalein was added is 0.1mol/dm^3. Thus, this shows a big difference when
1 mole of NaOH reacts with 1 mole of HOAc, and only phenolphthalein indicator can
be used to determine the range of weak acid pH7 – 11, and only phenolphthalein
indicator which has range of pH8-10 can be used to determine the end point.
Discussion:

In this experiment, we used electronic pH meter to determine the pH of

variety salts. Electronic pH meter is an electronic instrument measuring the pH
(acidity or alkalinity) of a liquid (though special probes are sometimes used to
measure the pH of semi-solid substances). A typical pH meter consists of a special
measuring probe (a glass electrode) connected to an electronic meter that measures
and displays the pH reading. It is an electrode system sensitive to the hydrogen ion
concentration in a solution is first dipped into a solution of known pH to calibrate the
instrument. Once calibrated, the apparatus can be used to measure the pH of any
other solution simply by immersing the electrode into it. Most modern pH meters
are able to determine pH values within 0.01 pH units, and research grade
instruments are capable of even greater precision in the pH range of 0.0 and 14.0.
When not in use, the glass probe tip must be kept wet at all times to avoid the pH
sensing membrane dehydration and the subsequent dysfunction of the electrode.
Occasionally (about once a month), the probe may be cleaned using pH-electrode
cleaning solution; generally a 0.1 M solution of hydrochloric acid (HCl) is used, having
a pH of about one.

Instead of pH value, we may define acidic, basic and neutral of one

substance. In pure water, that is a neutral,

[H+] = [OH-] = 1.0X10^-7 M

An acidic solution is one which [H+] is larger than 10^-7 M and so has a pH value that
less than 7.00. Thus, as a solution’s acidity increases, its pH decreases. A basic
solution is one in which the value of [H+] is less than 10^-7 M and so has a pH
greater than 7.00. As a solution’s acidity decreases, its pH increases.

pH < 7.00 - Acidic solution

pH > 7.00 – Basic solution

pH = 7.00 – Neutral solution

In part A, sodium chloride, NH4Cl solution was measured by an electronic pH meter

and determined its pH value is 5.20. Based on the pH concept, it belongs to acidic
solution as pH less than 7.00. Sodium Chloride, NH4Cl, is, in its pure form, a clear
white water-soluble crystalline salt of ammonia. The aqueous ammonium chloride
solution is mildly acidic. Sal ammoniac is a name of natural, mineralogical form of
ammonium chloride. The mineral is especially common on burning coal dumps
(formed by condensation of coal-derived gases), but also on some volcanoes.
Ammonium chloride is prepared commercially by reacting ammonia (NH3) with
(HCl). As these chemicals are corrosive, this process has to be performed in vessels
lined with nonreactive materials.

NH3 + HCl → NH4Cl

This reaction can occur if poorly sealed bottles of household ammonia (ammonium
hydroxide) and hydrochloric acid are stored in close proximity, leading to crystals
forming around the openings of the bottles (mostly appear on those leaking more
slowly). In the experiment, ammonium chloride dissolves in water and involves
decomposition into ammonia and hydrogen chloride gas.

NH4Cl → NH3 + HCl

Ammonium chloride dissolved in water becomes an acid. Hence, Ammonium

chloride can be used to produce low temperatures in cooling baths. For example, the
zero point of Fahrenheit temperature scale is determined by placing the
thermometer in a mixture of ice, water, and ammonium chloride. Besides,
ammonium chloride solutions with ammonia(NH3) are also can be used as buffer
solutions. In additional, ammonium chloride acts as a nitrogen source and is used in
fertilizers, as a feed supplement for cattle and as an ingredient in nutritive media for
yeast microbiological organisms in biological application. It is also used as a systemic
acidifying agent in treatment of severe metabolic alkalosis, in oral acid loading test
to diagnose distal renal tubular acidosis, to maintain the urine at an acid pH in the
treatment of some urinary-tract disorders.

An acid was described as a substance that produces Hydronium ions (H3O+) in

water, whereas a base gives OH-. An acid-base neutralization, according to
Arrhenius, is a reaction in which acid and a base combine to produce water and a
salt. For instance, when open bottles of concentrated hydrochloric acid and
concentrated aqueous ammonia are placed side by side, a white cloud forms when
vapours from the two bottles mix. The cloud consists of tiny crystal of ammonium
chloride which form when ammonia and hydrogen chloride gases, escaping from the
open bottles and mix in air and react.

NH3 + HCl → NH4Cl

The aqueous solution of ammonia (a base) is neutralised by an aqueous solution of

hydrogen chloride (an acid). Both involves the transfer of a proton (a hydrogen ion,
H+) from one particle to another, in water, where HCl is completely ionized, the
transfer is from H3O+ to NH3. The ionic equation is:

NH3(aq) + H3O+ (aq) + Cl- (aq) → NH4+ (aq) + Cl-(aq) + H2O(l)

Thus, ammonium chloride tends to be more acidic.

The strength of a Bronsted acid is referring to its ability to donate proton to a base.
The more complete the reaction, the stronger the acid. For instance, HCl and HNO3
react completely with water to give H30+ because they are strong proton donors.
However, acids such as HNO2, HC2H3O2, are much weaker proton donors. Their
reactions with water are far from complete and classify them as weak acids. In
similarly manner, the relative strength of bronsted bases are assigned according to
their abilities to accept and bind protons. Oxide ion react completely in water and
considered as strong base.

O2- + H2O → 2OH-

Weaker proton acceptors, such as ammonia, undergoes incomplete reactions with

water, we classify them as weak bases, in this experiment, Sodium Acetate
CH3COONa, and Sodium Formate HCOONa, are weak bases which have pH value of
8.15 and 7.27 respectively. However, Sodium Carbonate are stronger base than both
salts which has a pH value of 11.23.

Titration is a very useful laboratory technique in which one solution is used to

analyze another solution. The technique involves determining accurately the volume
of the standard solution needed to react exactly with a known volume of another
solution contained in a conical flask in a reaction for which the stoichiometry
reaction is known. In a titration, a burette is filled with a solution of known
concentration that will react with analyte. The reaction then is usually arrange to
result in colour change once the reaction is complete, the onset or disappearance of
colour indicating the end or titration which also known as the end point of solution
by adding small amounts of indicator.

In this experiment, burette was filled with 0.1mol/dm^3 of Sodium Hydroxide NaOH,
and react with the analyte- 10 cm3 of HCl in order to determine the volume of NaOH
used. By determine the end point, few drops of Bromophenol blue and
Phenolphthalein indicator was added and colour changes was observed. This process
was repeated by titrating 0.1mol/dm^3 of Sodium Hydroxide NaOH with 10 cm3 of
HOAc. Bromophenol blue indicator is an acid-base indicator with its useful range lies
between pH 3.0 and 4.6. It changes from yellow at pH 3.0 to blue at pH 4.6.
However, phenolphthalein indicator is an acid- base indicator with range lies
between pH 8-10. It changes from colourless pH8 to pink at pH10.

For the titration of sodium hydroxide and hydrochloric acid with different indicators,
the results obtained were quite similar with minor difference. This was a strong acid
and strong base titration, before and after the end point was reached, there was a
sharp increase in pH from pH 3 – pH 11. Any indicator that change colour within the
range can be used as the indicator of the titration. Phenolphthalein has pH range of
8 – 10 while Bromophenol blue has pH range of 3.0 – 4.6. Therefore both of the
indicators were suitable for the titration.

For the titration of sodium hydroxide and ethanoic acid with different indicator, the
results obtained were totally different. For weak acid and strong base titration, the
pH range before and after the end point was 7 – 11. Any indicators that change
colour within this range can be used as indicator for this titration. Only
phenolphthalein was suitable in the titration.

In a forward reaction, a formic acid molecule donates a proton to the water

molecules and changes to a formate ion, CHO2 -.

HCHO2 (aq) + H2O H30+ (aq) + CHO2-(aq)

Thus,HCHO2 behaves as a Bronsted acid, a proton donor. Because water accepts this
proton from HCHO2, water behaves as a Bronsted base, a proton acceptor. Two
substances that differ from each other by one proton are referred as to conjugate
acid-base pair. One member of the pair is called the conjugate acid because it is the
pair donor of the two. The other member is the conjugate base, because it is the
pair’s proton acceptor. So, H30+ Is the conjugate acid of the H20, and H20 is the
conjugate base of H30+.

The pair HCHO2 and CHO2- is the other conjugate acid-base pair. HCHO2 has more
H+ than CHO2-, thus, the conjugate acid of CHO2- is HCHO2, whereas the conjugate
base of HCHO2 is CHO2-. In the experiment, H2O + HOAc = H3O+ + OH-, HOAc
behaves as a Bronsted acid, a proton donor. Because water accepts this proton from
HOAc, water behaves as a Bronsted base, a proton acceptor. Thus, H3O+ Is the
conjugate acid of H20, and H2O iS the conjugate base of H30+. The pair of HOAc and
OH- is the othe conjugate acid-base pair. HOAc has more H+ than OH- , so, the
conjugate acid of OH- is HOAc, and the conjugate base of HOAc is OH-.

There are several precautions are needed to be taken in order to prevent incidents
occur during the experiment. We should always wear gloves when handle with acids
such as concentrated HCl. Besides, when we use an electronic pH meter, the glass
probe tip must be kept wet at all times to avoid the pH sensing membrane
dehydration and the subsequent dysfunction of the electrode. Occasionally (about
once a month), the probe may be cleaned using pH-electrode cleaning solution;
generally a 0.1 M solution of hydrochloric acid (HCl) is used, having a pH of about
one.
Conclusion:

The pH value for ammonium chloride NH4Cl, Sodium Acetate CH3COONa,

Sodium Formate, HCOONa, and also Sodium Caronate Na2CO3 are 5.20, 8.15, 7.27,
11.23 respectively. The degree of hydrolysis of NH4+ is 1.41x10^-6. In a titration
process, strong acid reacts with strong base, both phenolphthalein and Bromophenol
Blue indicators are suitable to indicate their end point whereas for a weak acid reacts
with strong base, only phenolphthalein indictor is suitable to determine their end-
point.

References:

1. James E.Brady, Federick A.Senese, Neil D. Jesperson (2009). Chemistry

International Student Version, Fifth Edition, John Wiley & Sons (Asia) Pte.Ltd.
(Page 606-634)

2. Eng Ngaun Hong, Lim Eng Wah, Lim Yean Ching (2007). Chemistry. Penerbitan
Pelangi Sdn.Bhd. (Page 220-229)

3. Averil Eldredge(2007) Chemistry Principles, Patterns, and Applications.

Pearson International Edition. (Page 721-803)

4. Ralph H. Petucci, William S. Harwood, F.Geoffrey Herring, Jeffry D.

Madura(2007,2002,1997). Genearl Chemistry Principles and Modern
Applications, Ninth Edition, Pearson International Edition (Page 664-695)