ACIDS AND BASES AND SOLUBILITY EQUILIBRIA

A Project Presented to the Faculty of

AMA Computer College Bacolod

Bacolod City

In partial fulfillment of the requirements to the Degree Bachelor of Science in Information

Technology

in the Course - General Chemistry

By:

Katherine Anne L. Ortiz

Mycah Cabu-al

March 17, 2019

Table of Contents

Page Number

Table of Contents …………………………………………………………………. 1

Introduction of the Acids and Bases and Solubility Equilibria ……..……………. 2

Concepts of Acids and Bases …………………………………………………….. 3

The Acid-Base Properties of Water ………………………………………………. 7

pH as a Measure of Acidity ……………………………………………………..... 9

Strengths of Acids and Bases …………………………………………………….. 11

Diprotic and Polyprotic Acids ……………………………………………………. 16

Molecular Structure and Strengths of Acids ……………………………………… 18

Acid-Base Properties of Salts …………………………………………………….. 20

Acid-Base Properties of Oxides and Hydroxides ……………………………….... 23

Common Ion Effect ………………………………………………………………. 24

Buffer Solutions …………………………………………………………………… 25

Titration of Acids and Bases …………………………………………………….... 26

Solubility Equilibria ………………………………………………………………. 29

Conclusion ……………………………………………………………………….... 30

Definition of Terms ……………………………………………………………….. 32

Sample Experiments ………………………….……………………………....….... 35

References and Supplementary Materials .……………………………………....... 46

Introduction of the Acids and Bases and Solubility Equilibria

Acids and bases are not simply topics in a Chemistry class. In fact, most of the things

around us can be classified as an acid or as a base, and they have a lot of uses at home, in

industrial facilities, in food, and even in our bodies. The most common acids and bases are found

in the simplest items. Citric acid and ascorbic acid are found in fruits and vegetables. Acetic acid

is the main component of vinegar. Sodium hydroxide is a key component in soap manufacturing.

Sodium bicarbonate, fondly known as baking soda, is a great multi-purpose cleaner. These items

have purposes that are affected by their acidity or basicity, and in this module, we will learn

about the concepts of acids and bases.

Figure 1. The blueberry thrives on acidic soil with a pH range of about 4.0 to 5.0; http://www.rodalesorganiclife.com/garden/blueberries; Apr 24,

2017

For thousands of years people have known that vinegar, lemon juice, and many other

foods taste sour. However, it was not until a few hundred years ago that it was discovered why

these things taste sour – because they are all acids. The term acid, in fact, comes from the Latin

term acere, which means "sour". While there are many slightly different definitions of acids and

bases, in this lesson we will introduce the fundamentals of acid/base chemistry.

In the seventeenth century, the Irish writer and amateur chemist Robert Boyle first

labeled substances as either acids or bases (he called bases alkalies), according to the following

characteristics:

 Acids taste sour, are corrosive to metals, change litmus (a dye extracted from

lichens) red, and become less acidic when mixed with bases.

 Bases feel slippery, change litmus blue, and become less basic when mixed with

acids.

 While Boyle and others tried to explain why acids and bases behave the way they

do, the first reasonable definition of acids and bases would not be proposed until

200 years later.

Concepts of Acids and Bases

 Arrhenius acids are compounds containing hydrogen, and when dissolved in water,

releasing this hydrogen ion (H+) in an aqueous solution. On the other hand, Arrhenius bases are

compounds that release hydroxide ions (OH-) when dissolved in water. Hydrochloric acid and

sodium hydroxide are examples of an acid and a base, respectively. Their dissociation in an

aqueous solution is as follows:

HCl +  H O →  H + Cl
2
+ -
(1)

NaOH  + H O → Na + OH
2
+ -
(2)

The Arrhenius concept can explain the similar properties of acids (the ability to produce

H+) and bases (the ability to produce OH-). However, this theory is only applicable for solutions

in water or in aqueous solutions and does not account for bases not containing the hydroxide ion

(e.g. ammonia, NH3).

Svente Arrhenius, a Swedish scientist, proposed that compounds separate into their

individual ions as they dissolve in water. He also suggested that compounds containing hydrogen

would release this ion when dissolved in water.

When an Arrhenius acid reacts with an Arrhenius base, it will yield water and salt,

commonly referred to as the neutralization reaction.

The Brønsted-Lowry Concept offers a more general definition of acids and bases. A

Brønsted-Lowry acid is a substance capable of donating a proton (H+) while a Brønsted-Lowry

base is a substance capable of accepting a proton. Consider the dissolution of gaseous

hydrochloric acid in water.

 Notice that the reaction yields (right side of the equation) a chloride ion and a water

molecule with an additional hydrogen molecule. This positively charged ion is called the

hydronium ion (H O ). Based on the Brønsted-Lowry concept, HCl is the acid (proton donor)
3
+

and H O is the base.

2

In comparison to the Arrhenius model, the Brønsted theory is not limited to hydroxide-

containing bases but also considers neutral compounds such as water.

Take a look at the reaction below,

We can identify that the base, ammonia (NH3), accepted a proton and produced an

ammonium ion (NH4 +) while water acted as the acid and donated a proton. In the previous

example, water acted as a base, and on this reaction, it acted as an acid. When a substance can

act both as an acid and as a base, it is said to have amphoteric properties. This topic will be

discussed later in this module.

Another concept included in the Brønsted-Lowry model is the conjugate acid-base

pairing – an acid and its conjugate base, or a base and its conjugate acid. A conjugate acid can

be defined as the substance formed when the base accepted the proton. A conjugate base is the

substance formed after the acid loses its proton. Consider the complete dissociation of
hydrochloric acid in water (3). The conjugate base is the chloride ion (Cl-) and the conjugate

acid is the protonated water (H O+). The identification of the conjugates is simply by definition.
3

Now, let’s consider the dissociation of ammonia in water. Notice that this reaction is

reversible. This means that the reaction can proceed from the left side to the right of the reaction

or vice-versa, depending on the conditions of the reaction. This also means that we have two

reactions in a single solution and we can identify four sets of conjugate acid-base pairs as

follows:

The numbers help designate the conjugate pairs. For example, if water is considered the

acid, then its conjugate base will be the hydroxide ion. If the ammonium ion is considered as

acid, then the conjugate base will be ammonia. We can identify the conjugates by following

these guidelines:

1. The conjugate base has one less H atom than its corresponding acid.

2. The conjugate acid has one more H atom than its corresponding base.

3. The conjugate base has one less positive or one more negative charge than its

corresponding acid.
 4. The conjugate acid has one more positive or one less negative charge than the

corresponding base.

When an acid or a base reacts with water, the reaction is called ionization. Depending on

the reacting species, it can be specified as an acid or base ionization.

The Acid-Base Properties of Water

Earlier, we used water as an example for both acid and base. Those reactions demonstrate

the amphoteric capability of water. An amphoteric compound is a substance that can behave as

either an acid or as a base, and water is the most common example. If water reacts with acids

such as hydrochloric acid, it acts as a base, and if it reacts with bases like ammonia, it functions

as an acid. If we look at the dissociation of water,

one water molecule (green) acts as an acid and donates one hydrogen atom to another water

molecule (black), which acted as a base and accepts the hydrogen atom. This reaction is called

the autoionization. We can also apply here the concept of conjugates wherein the pairs are: (1)

water (acid) – hydroxide ion (base), and (2) hydronium ion (acid) – water (base).

In previous lectures, you have learned chemical equilibrium and how it can be used to

determine the concentration of the compounds in a reaction. If we consider the autoionization of

water, we have

2H O  ⇋ H O + OH
2 (1) 3
+ -
(aq)
 Using the equation above, we can calculate for the equilibrium constant,

K = [H O ][OH ]
c 3
+ -

Since Kc is the indication for equilibrium constant, we can replace it with Kw to specify

that the constant is for the autoionization of water. At the same time, we can replace [H O ] with 3
+

[H ], to indicate a proton in aqueous solution.

+

K = K = [H ][OH ]
c w
+ -

Kw can be defined as the product of the molar concentrations (usually represented by

“[ ]”) of the hydronium ion and the hydroxide ion. At 25°C, the molar concentrations of H and +

OH are equal when in equilibrium.

-

[H ] = [OH ] = 1.0 × 10 M
+ - -7

By substituting Equation (9) to Equation (8), we can calculate

K = (1.0×10 )(1.0×10 ) = 1.0×10

w
-7 -7 -14

And this value will hold true for pure water or any aqueous solution at 25°C. If we

consider varying conditions at 25°C,

1. neutral solution, [H ] = [OH ]

+ -

2. acidic solution, [H ] > [OH ]

+ -

3. basic solution, [H ] < [OH ]

+ -

in all cases, K will always be equal to 1.0×10 .

w
-14

pH as a Measure of Acidity
 In actuality, the concentration of H is very small. The pH scale was developed to provide
+

an easier way to determine whether a solution is acidic, basic or neutral. It is a logarithmic scale

(base 10) where

pH = −(log[H ]) +

Consider the concentration of H+ in Equation (9), if we calculate for its pH,

pH = −(−7.00) = 7.00

Because pH is calculated as a log base 10, for every power of 10, the pH changes by 1. It

is also important to remember that as the [H ] increases, the pH decreases.

+

So how do we identify whether a solution is acidic or basic using the pH scale?

1. The solution is neutral if [H+] = 1.0×10 , pH = −(log(1.0×10 )) = 7.00

-7 -7

2. The solution is acidic if [H+] < 1.0×10 , pH < 7.00 -7

3. The solution is basic if [H+] > 1.0×10 , pH > 7.00 -7

The actual pH of solution can be determined using a pH meter, up to at least two decimal

places. It can also be estimated using pH papers. Figure 2 shows examples of a pH meter and

paper. Figure 3 shows a list of common items and where they fall within the pH range.

Figure 2.pH meter and pH indicator strips;http://chemphys.armstrong.edu/yroach/MultimediaProject/webpages/pHmeter.htm

Figure 3.pH levels of common items; http://drwillard.com/blog/wpcontent/uploads/2015/09/pHscale.gif; Apr 24, 2017

There will be cases where instead of [H+], [OH-] will be given. Applying the same

principles as pH, pOH can also be calculated using the formula

pOH = −(log[OH ]) -

Using Equations (10) and (11), the relationship between pH and pOH can be expressed

mathematically, as shown below,

Kw = (1.0×10 )(1.0×10 ) = 1.0×10

-7 -7 -14

−(log[H+]) +−(log[OH-]) = −(log(1.0×10 )) -14

pH+ pOH = 14.00

Strengths of Acids and Bases

Strong acids are acids that completely dissociate or ionize in water. Examples of strong

acids are the inorganic types, including hydrochloric acid (HCl), nitric acid (HNO3), sulfuric

acid (H SO ) and perchloric acid (HClO ).

2 4 4
 Strong bases, in similar context, are bases completely ionized in water. Examples are the

hydroxides of Group 1 (alkali) metals. The most common examples are sodium hydroxide

(NaOH) and potassium hydroxide (KOH).

Weak acids are acids that ionize to limited extent and at equilibrium, the resulting

solution will be a mixture of the ionized and unionized forms of the acid. Examples of weak

acids are mostly organic acids such as acetic acid (CH COOH), citric acid (C H O ) and ascorbic
3 6 8 7

acid (C H O ).
6 8 6

Weak bases have similar properties to weak acids. Examples are ammonia (NH ), 3

ammonium hydroxide (NH OH) and methylamine (CH NH ).

4 3 2

Table 1. Conjugate acid-base pairs and their relative strengths

The strength of acids and bases and their conjugates are inversely proportional.

Hydrochloric acid, a strong acid, dissociates to yield the hydronium ion (H O ) and Cl- . Since the
3
+

relationship is inverse, the conjugate base, Cl- , has relatively very little strength, thus a very

weak base.

In an aqueous solution, if an acid reacting with water is stronger than H O , it will 3

+

continuously react with water to produce H O . This means that in a reaction with an excess of
3
+
water, the strong acid will completely ionize to form H O . If the acid is weaker than H3O+, the
3
+

reaction to producing H O proceeds less, and the starting acid remains in the solution. The same
3
+

concept is also applicable for bases, only this time, the bases are compared to OH- .

Weak acids and bases ionize to a limited extent when reacted with water. In fact, most

acids are classified as weak acids. The dissociation of an acid can be calculated using the

equilibrium expression. In the previous lecture, the ionization of a strong acid is an irreversible,

depicted by a single-headed arrow.

Weak acids dissociate differently.

Consider a weak acid, HA. The dissociation of this acid can be represented as

The equilibrium concentration for the dissociation of HA, also called acid ionization

constant K , can be expressed as

a

The acid ionization constant is used to measure the strength of an acid. A strong acid has

a higher Ka while weak acids have relatively low Ka. This is because, at equilibrium, strong
acids produce more H3O+. However, since strong acids are expected to dissociate completely,

the acid ionization constant will be more applicable to weak acids.

When dealing with Ka, it is possible to either calculate for the concentration of the

present species in the aqueous solution, or determine the pH of the solution. Either way, through

this module, we will learn the basic approach/strategy on how to deal with ionization constants.

Suppose we are asked to calculate for the pH of a 0.5M HNO2 solution at 25°C. The Ka

for nitrous acid, given in Table 2, is 4.6×10-4. The first step is to write the ionization equation

for nitrous acid and identify the compounds that will be present in the solution at equilibrium

Since we know that nitrous acid is a weak acid, not all of it will ionize into H O and NO
3
+
2

- . At equilibrium, HNO2 will still be present and its concentration must be considered in the

calculation. Using Equation (13),

Write a summary of the changes in the concentration of the present species, as you would

in a chemical equilibrium equation.

Substitute the calculated values for each species

Rearranging the equation

x + (4.5×10 )x + 2.25×10 = 0
2 -4 -4

A quadratic formula can be used to calculate for x, however, if we assume that the value

of x is very small compared to the initial concentration, we can approximate that if x <<< 0.50,

then 0.50 – x ≈ 0.50. Substituting this value to the Ka expression,

Now that we have the value of x, we can now calculate for the concentration of the

species at equilibrium,

[HNO ] = 0.50−x = 0.50 – 0.015 = 0.485 M

2

[H O+] = x = 0.015 M
3

[NO ] = x = 0.015 M
2-

pH = −(log 0.015) = 1.82

For weak bases, we use the term base ionization constant, K . To solve for the pH of the
b

solution or the species in a weak base solution, we can follow the same steps we used for K but a

instead of determining pH, pOH will be calculated. Then using Equation (12), you can calculate

for pH.

At the start of this module, we learned that a weak acid has a corresponding conjugate

base. We also now know how to calculate for K and Kb. Consider the general dissociation
a

equation of weak acid HA again

HA + H O  ⇌ H O
(aq) 2 (l) 3
+
(aq) +A -
(aq)
 A-
(aq) + H O ⇌ HA + OH
2 (l) (aq)
-
(aq)

HA is the weak acid and its conjugate base is A- . Suppose we calculate for the ionization

constants.

K = [H O ][A-]/[HA]
a 3
+
K = [HA][OH ]/[A ]
b
- -

Let’s take the products of the ionization constants. Note that [A ] and [HA] cancel out and -

we will be left with

K K = [H O ][OH ]
a b 3
+ -

which is also equivalent to the ionization constant of water K . w

For any conjugate acid-base pair, it is always true that

K = KK.
w a b

Diprotic and Polyprotic Acids

All the examples of chemical equations are ionization of monoprotic acids. These acids

can donate a single proton, hence, mono-. However, there are acids that has more that one proton

to donate: diprotic (two protons) and polyprotic (more than two protons) acids. While the

calculations involved with these acids are similar to the monoprotic acid, it is not as

straightforward because diprotic and polyprotic acids lose one proton at a time. This means a

diprotic acid will have two ionization reactions, while a polyprotic acid can have as many as its

proton available for donation.

Figure 4.The ionization reactions of carbonic acid and the formula for its two ionization constants.

The calculation for the ionization constant follows the same steps. However, it is

important to carefully identify the species present in the solution and their functions. In the figure
above, the acid for the first reaction is carbonic acid and its conjugate base is the bicarbonate ion.

For the second reaction, the conjugate base becomes the acid and the conjugate base is a

carbonate ion. By identifying the acids in the reaction, you will be able to select the appropriate

K.
a

Table 2. Ionization constants

 Molecular Structure and Strengths of Acids

Recall the acid ionization constants of weak acids. Note that the temperature is indicated

– at 25°C. This means that at different temperatures, the value of the K also differs.
a

There are many factors affecting the strength of acids and how much ionization they

would undergo. Some of these factors are temperature, the type of solvent used, and the

molecular structure of the acids.

Let us consider acid, HA. We know from studying chemical bonds that the stronger the

bond, the more difficult it is to break the atoms apart. The same is true for acids. If the H−A

bond is too great, the release of the hydrogen atom will be very difficult, and the acid would not

want to “donate” more of its H , hence, the weaker the acid. Another factor based on the structure
+

is the polarity of the H−A bond. If the bond is highly polar, that is, the partially positive charge

greatly accumulates towards the H-atom and the partially negative charge towards the A-atom,

then the acid has a higher tendency to produce H and A , thus, a stronger acid. Stronger acids
+ -

have high polarity.

Let us now look at some examples. The binary acids from halogens are called

Hydrohalic acids, which include HF, HCl, HBr and HI. To identify which are strong acids and
which are weak acids, we should consider the strength of the bonds present. According to Table

__, the bond enthalpy from HF to HI (going down the Halogen group) is decreasing. This means

that the energy to break the bond between H-atom and the halogen decreases. Based on this, HI

will be the strongest acid and HF will be the weakest. If we also look at the polarity of the bond,

we know that F is the most electronegative atom in the periodic table, and the trend for

electronegativity decreases down the group. If we consider this, HF would be the strongest acid,

and HI will be the weakest. We then have conflicting assumptions. For this case, though, the

trend based on bond enthalpy was correct.

HF < HCl < HBr <HI

For oxoacids, or acids that contain hydrogen, oxygen and one other element as the central

atom. They are also characterized by one or more O−H bond. This O−H bond becomes more

polar if the central atom is highly electronegative or has high oxidation state, thus, making it a

stronger acid. When comparing oxoacids with central atoms from the same group (e.g.

halogens), they have the same oxidation state. We can then compare their strength by their

electronegativity, so

HClO > HbrO

3 3

Oxoacids with the same central atom but different numbers of attached groups can be

compared based on the oxidation number. The higher the oxidation number of the central atom,

the stronger the acid.

The strength of carboxylic acids is determined by the nature of the R-group. If the R-

group is highly electronegative, it pulls the electron density towards the R-group away from the
O−H. This means the O−H group becomes more polar. Thus, the more electronegative the R-

group, the stronger the acid.

Acid-Base Properties of Salts

In the Arrhenius concept of acids and bases, we defined neutralization as the reaction

between an acid and a base, producing water and salt. Salt is a compound made up of a cation

(positively-charged ion) and an anion (negatively-charged ion) joined together by an ionic bond,

hence, an ionic compound.

Although salts in general are neutral compounds, when they are dissolved in water, the

ions produced may affect the overall pH of the solution. Let’s look at different examples to see

how this change in pH may occur.

1. Salts containing an alkali or alkaline earth metal + the conjugate bases of strong acids.

When NaOH reacts with HCl, it forms the salt NaCl. When in water, NaCl dissociates

completely as

Na , a cation, neither accepts nor donates H . Cl is the conjugate base of HCl and is less likely to
+ + -

accept H ions. Therefore, the pH of the solution remains unchanged, or neutral.

+

2. Salts formed by reacting a strong base with a weak acid.

Consider the neutralization reaction between NaOH (strong base) and CH COOH (weak acid).
3
When sodium acetate dissolves in water, it will produce a basic solution. Take a look at the

dissociation then hydrolysis reactions of the salt

Because acetate is a conjugate base of a weak acid, it has a strong affinity for H ions. It
+

will accept hydrogen from water and yield acetic acid and hydroxide ion. Since the solution

produced OH , the solution becomes basic.

-

3. Salts formed by reacting a strong acid with a weak base.

Consider the neutralization reaction between HCl (strong acid) and NH3 (weak base).

When ammonium chloride dissolves in water, it will produce an acidic solution, as shown in the

following reactions

Since NH is a weak base, its conjugate acid, NH , is a relatively strong acid. It will function as
3 4
+

an acid in the reaction, donating H+ to water to yield ammonia and H O . Therefore, the resulting
3
+

solution is acidic.

4. Salts from reacting a weak acid with a weak base

If the salt is produced from the neutralization of weak acids and bases, this means the cations and

anions produced will both undergo hydrolysis (reaction with water). In this case, we will need

the ionization constants of the reacting species and follow these guidelines:

a. K > K : If K is higher than K , this means the anion (or the base in the reaction) has stronger
b a b a

affinity for the hydrogen-donating water, hence, [OH ] will be higher than the [H O ]. The
-
3
+

solution will be basic.

b.K < K : If  K is lower than K , this means the cation (or the acid in the reaction) has a higher
b a b a

tendency to donate a hydrogen atom, hence, [H+] will be higher than the [OH-]. The solution

will be acidic.

c. K ≈ K : The solution will be relatively neutral.

b a

Table 3. Acidity of Salt Solutions

Acid-Base Properties of Oxides and Hydroxides

Oxides of alkali and alkaline earth metals, except for Beryllium, produce basic solutions

when hydrolyzed.
 The hydrolysis reaction yields the hydroxides of the metals, which are strong bases.

Oxides of nonmetals with high oxidation numbers produce acidic oxides. Some examples are

The reaction between gaseous sulfur trioxide and water is the primary source of acid rain.

Amphoteric oxides, like water, can function either as a base or an acid. Examples are BeO, Al O ,
2 3

Ga O , SnO , and PbO .

2 3 2 2

Hydroxides of the alkali and alkaline earth metals are basic, and the most common

examples are NaOH and KOH. Hydroxides of Be, Al, Sn, Pb, Cu, Zn and Cd are amphoteric and

these compounds are insoluble.

Common Ion Effect

Suppose we have a solution containing more than one solute (acid, base, salt). What

would be the effect of this additional solute to the equilibrium and pH of the solution?

In an acid-base reaction, it is possible to have more than one solute, and they can even

have the same ion. The addition of the common ion shifts the reaction from the product side
(ions) to the reactant side (acid). For example, let’s consider the addition of sodium acetate to the

ionization reaction of acetic acid.

The addition of acetate increases the [CH COO ] already present in the acetic acid
3
-

reaction mixture. Based on Le Châtelier’s Principle, a chemical reaction proceeds from a system

of higher concentration to lower concentration. The equilibrium is disrupted and the

concentration of H decreases. Hence, in the presence of a common ion, the solution becomes
+

less acidic.

The common ion effect, in general, is the shift in equilibrium of a reaction caused by the

addition of a common ion. This also affects the pH of the solution. Using the Henderson-

Hasselbalch Equation (15),

The Henderson-Hasselbalch equation is derived from equilibrium constants. It is

temperature-dependent and will vary depending on the temperature of the solution. Regardless of

the source of the common ion, this equation can be used to calculate for the pH of the solution.

Buffer Solutions

Another application of acids and bases is the preparation of buffer solutions. Buffer

solutions are highly important not only in chemical processes but also in biological systems like
the human body. Buffers are solutions of weak acids/bases and their conjugate salts, and are able

to resist drastic changes in pH when additional acid or base is added.

A buffer works by “counteracting” with the added OH- or H+. For it to withstand the

changes, it must contain high concentrations of both acids and bases. However, these acid and

bases must not neutralize each other. The best components for buffer preparation are weak acids

and their conjugate bases, usually from the salt form.

Buffers are usually prepared with the final concentration and pH already identified. It is

also important to remember that buffers should contain almost equal concentrations of acid and

conjugate base. Thus, it is practical to work backwards using the Henderson-Hasselbalch

equation.

Assuming [acid] ≈ [conjugate base],

To prepare the buffer, we should choose the weak acid with a pKa closest to the needed

pH.

Titration of Acids and Bases

There are four types of acid-base titration and we will briefly discuss each. The first

titration is between a strong acid and a strong base. This reaction is a neutralization reaction, as

shown in the sample chemical equation, using HCl and NaOH as example.
 As we have learned before, Na+ and Cl- do not affect the acid-base reactions. Hence,

considering only the species involved in acid-base reaction, we have

Let’s take a look at a pH profile or the titration curve determined from the titration of a

strong acid with a strong base.

Figure 5.Sample titration curve.A strong base run into strong acid.

At the initial point, the pH of the analyte (strong acid) is very low. When the titrant

(strong base) is added, the pH slowly increases. The increase begins to speed up near the

equivalence point, and will slowly increase again. The equivalence point is reached when the

amount of acid is equivalent to the amount of base.

The second titration is a strong acid against a weak base. At the beginning of the adding a

strong acid to a weak base, the pH change is more obvious compared to a strong acid-strong base

system. However, it will reach a point where the change in pH is lower, meaning, the plot is less

steep. At this point, in addition to the weak base and strong acid, the conjugate acid of the weak

base is now part of the solution. A mixture of a weak base and its conjugate, as we have learned
previously, is a buffer. That is why the pH change is less. Upon addition of excess acid, a drastic

fall in pH will again be observed, signaling the equivalence point.

Figure 6.Titration of a weak base with a strong acid. The equivalence point is lower than 7 (neutral).

The third titration setup is between a strong base and a weak acid. If we titrate a weak

acid with a strong base, the initial pH change will be drastic, and eventually the change will be

less (similar to the weak base-strong acid mixture). The equivalence point will be higher than

neutral.

Figure 7.Titration of a srong base with a weak acid base.

The fourth titration system is the reaction between a weak acid and a weak base. Since

the reacting species are both weak, the equivalence point is almost at pH 7. This titration

produces both the conjugates for the weak acid and base, and that means, the final solution has a
tendency to act as a buffer. That is why, in weak acid-weak base titration, you cannot find the

steep point when equivalence point is almost reached.

Figure 8.Titration curve from the reaction of a weak base with a weak acid.

In the titration of polyprotic acids, the equivalence point is based on the number of

protons it can accept or donate. Sodium carbonate Na CO , for example, when in aqueous
2 3

solution, releases Na and CO

+
3
2-
(carbonate). The anion can accept two hydrogen atoms and will

have two equivalence points in the titration curve. Phosphoric acid is a triprotic acid; it will have

3 equivalence points.

Solubility Equilibria

Solubility is a physical property referring to the amount of solute dissolved in water to

achieve a saturated solution. It can be expressed in several terms such as solubility (g/L) or molar

solubility (M).

Like the ionization reaction, the solubility equilibrium depends on a constant. The

solubility product constant or Ksp is calculated as follows

K = [products]/[reactant]
sp

Solubility equilibrium is reached when there is no change in the concentration of the

product and reactants. The solubility equation for salts is similar to the ionization of weak acids

and bases: not complete dissociation.

 The solubility equilibrium is also affected by several factors, but for this module, we will

look at how the common ion and pH affects solubility.

The common ion effect disrupts equilibrium and shifts the direction of the reaction.

Consider the dissociation of NaCl. This will produce Na and Cl . At equilibrium, without other
+ -

species present, the direction of the reaction is from the left to right (reactants to products). If

you add a solution containing Cl- , the direction of the reaction will still be towards the ionic

forms, but this time, the amount that can be dissolved is less than when we used pure water. The

addition of a common ion will lead to lower solubility.

The pH of the solution also affects the solubility. When the anion of the slightly soluble

salt is basic, the solubility increases with an increase in hydrogen atom. The solubility of salts

with anions from strong acids is not affected by pH changes

As long as you know the correct equation for the dissolution of a slightly soluble salt, you

can analyze the effect of any outside factor by following the Le Chatelier’s principle.

Conclusion

With these experiments, you saw that there are acid substances and basic substances.

They react with each other, producing salts. The acid-basic degree is expressed in pH. To

measure the acid-basic degree of a substance, you can use pH papers like litmus paper, indicators

like phenolphthalein, and electronic pH meters. Many other natural substances of vegetable

origin have the property to change color because of the acidity of the environment. We used the

juice of the red cabbage as an indicator and we obtained pH papers. We determined the color

scale of these papers. You saw how the phenolphthalein changed color when it gets over a pH

threshold. We exploited the properties of this indicator to determine with precision the acidity of
vinegar. You can continue with experiments of this kind, for example by titrating other liquids,

by looking for natural indicators among herb teas, plants, flowers, fruits, berries, etc.

As you know, the aim with which we propose laboratory activities is not only to get

amusement, but also to arouse curiosities which then stimulate a deeper study of the matters we

touched. For this reason, we hope you do not limit yourself to the operational aspects of these

experiments, but try also to take the occasion to study a text of inorganic chemistry to acquire its

basic concepts. The knowledge you will gain will allow you also to continue with experiments

like these, getting further amusement and knowledge. In fact, it is clear that you can benefit

much more from activities of this type, when you have learned what are atoms, molecules,

valence, the different types of solutions, electrolytic dissociation, and other basic concepts of

chemistry. In the Bibliography you will find sources to help advance your knowledge of the

exciting subject of chemistry!

Definition of Terms

Acid - a chemical substance that neutralizes alkalis, dissolves some metals, and turns

litmus red; typically, a corrosive or sour-tasting liquid of this kind. CHEMISTRY - a

molecule or other entity that can donate a proton or accept an electron pair in reactions.

Amphoteric substance - a substance that has the ability to act either as an acid or a base

Arrhenius acids - any substances that increases the concentration of hydronium ions

(H O ) in solution.
3
+

Arrhenius bases - any compound that donates an hydroxide ion (OH ) in solution.
–
Autoionization of water, and Autodissociation of water -  is an ionization reaction in

pure water or in an aqueous solution, in which a water molecule, H O, deprotonates (loses

2

the nucleus of one of its hydrogen atoms) to become a hydroxide ion, OH . The hydrogen
−

nucleus, H , immediately protonates another water molecule to form hydronium, H O .

+
3
+

Bases - CHEMISTRY - a substance capable of reacting with an acid to form a salt and

water, or (more broadly) of accepting or neutralizing hydrogen ions.

Brønsted-Lowry acid - any substance that can act as a proton donor

Brønsted-Lowry base - any compound capable of accepting a proton

Buffer solution - (more precisely, pH buffer or hydrogen ion buffer) is an aqueous

solution consisting of a mixture of a weak acid and its conjugate base, or vice versa.

Common-ion effect - is used to describe the effect on an equilibrium involving a

substance that adds an ion that is a part of the equilibrium.

Conjugate acid - is a chemical compound formed by the reception of a proton (H ) by a +

base—in other words, it is a base with a hydrogen ion added to it.

Conjugate acid - base pairing - Two molecular species that easily transfer a hydrogen

ion between them,especially from the acid to the base

Conjugate base - is what is left over after an acid has donated a proton during a chemical

reaction.

Diprotic Acid - is an acid that can donate two proton or hydrogen atom per molecule to

an aqueous solution.

Hydrohalic acid - Any acid formed from a binary compound of hydrogen and a halogen.
Ionization or ionisation - is the process by which an atom or a molecule acquires a

negative or positive charge by gaining or losing electrons, often in conjunction with other

chemical changes.

Neutralization Reaction - A neutralization reaction is when an acid and a base react to

form water and a salt and involves the combination of H+ ions and OH- ions to generate

water.

Oxoacids or oxyacid - is an acid that contains oxygen.

pH scale - is a scale used to specify how acidic or basic a water-based solution is.

Polyprotic acids - are specific acids that are capable of losing more than a single proton

per molecule in acid-base reactions.

Solubility - is a physical property referring to the amount of solute dissolved

in water to achieve a saturated solution.

Solubility equilibrium - is reached when there is no change in the

concentration of the product and reactants.

Strong acids - are acids that completely dissociate or ionize in water.

Strong bases - in similar context, are bases completely ionized in water.

Titration curve - is a graphical representation of the pH of a solution during a titration.

Weak acids - are acids that ionize to limited extent and at equilibrium, the

resulting solution will be a mixture of the ionized and unionized forms of the

Acid.

Weak bases have similar properties to weak acids.

Sample Experiments

SOLUBILITY AND THE SOLUBILITY PRODUCT CONSTANT

MATERIALS:

100 mL beakers (3); 25 mL pipet; 50 mL burets (2); 125 mL Erlenmeyer flask (2); filter

funnel; 5” filter paper; phenolphthalein in dropper bottles; standardized ~0.025 M NaOH

solution; saturated solution of KHC H O which is also 0.0150 M in NaCl; saturated

4 4 6

solution of KHC H O which is also 0.0150 M in KCl.

4 4 6

PURPOSE:

The purpose of this experiment is to determine a solubility product equilibrium constant,

K , and to distinguish the K from the solubility.

sp sp

LEARNING OBJECTIVES:

By the end of this experiment, the student should be able to demonstrate the following

proficiencies:

1. . Determine the value of a Ksp equilibrium constant in the presence and absence

of a common ion.

2. Experimentally distinguish between the solubility and the solubility product

constant.

3. Use an acid-base titration to quantitatively determine the amount of a weak acid

present in solution.

4. Understand the common ion effect.

DISCUSSION:
 Many ionic compounds, such as NaCl, readily dissolve in water, but others have quite

limited solubility. The solubility of a salt is the quantity or amount present in some volume of

saturated solution, one for which an equilibrium exists between the pure solid and its dissolved

and dissociated ions. Solubilities can cover a wide range of values, e.g. 36 g/100 mL (6.1 M) for

NaCl, and 0.00019 g/100 mL (1.3 x 10-5 M) for AgCl, both at 25 C. Substances on the low end
o

of the solubility range, say ≤ 0.01 M, are often described as being “insoluble” salts.

The equilibrium that exists in saturated solutions of insoluble salts is called a solubility

equilibrium, and the equilibrium constant for that case is called the solubility product constant, or

K . For AgCl, these have the form

sp

AgCl (s) ⇌ Ag (aq) + Cl (aq)

+ −
Ksp = [Ag ] [Cl ] = 1.8 x 10 @ 25 C           (1)
+ − −10 o

The K is an ordinary equilibrium constant, and can be treated with the usual equilibrium tools,
sp

such as the I.C.E. (Initial, Change, Equilibrium) table for quantitative calculations. Like other

equilibrium constants, it depends only on the temperature, and not on the concentrations of other

dissolved substances. Unlike the K , the solubility (how much dissolves) does depend on the
sp

presence of other substances in solution, especially for “common ions”, those dissolved ions

common to both the insoluble salt and another compound. It is easy to see how this works by

applying LeChatelier’s Principle to the equilibrium of equation 1. If we start with a saturated

solution of AgCl, and add the soluble salt NaCl to the solution, the NaCl will dissolve and

increase the [Cl ]. By LeChatelier’s Principle, the reaction equilibrium will shift left, resulting in
−

a larger amount of the solid (undissolved) AgCl. Thus the solubility of AgCl will decrease. Since

the temperature remains constant, the Ksp is unchanged by that action. These features are

reconciled when we recognize that the [Cl ] term in the Ksp expression of equation 1 includes
−
chloride ion from all sources, not just the dissolution of AgCl. Adding NaCl increased the

chloride ion concentration, so the [Ag ] had to decrease, by precipitating out some AgCl (s).
+

Ksp values are often quite difficult to measure, because the concentrations of the

substances involved are very small. A common way to determine them is by a precipitation

titration, where one adds reagent while looking for the faint evidence of formation of the

insoluble salt, signaling that the solution has become saturated. In this experiment we can use an

alternate approach, because one of the ions of the insoluble salt is acidic. We can thus perform a

(much easier) acid-base titration to determine the amount of that ion, and obtain the Ksp from

that.

The insoluble salt for this experiment is potassium hydrogen tartrate, KHC4H4O6. (This

substance is well-known in kitchens as “cream of tartar”, and is also an ingredient in baking

powder.) The solubility equilibrium for potassium hydrogen tartrate is

KHC H O (s) ⇌ K (aq) + HC H O (aq)

4 4 6
+
4 4 6
−
Ksp = [K+][HC H O ] (2)
4 4 6
−

In the absence of any other source of potassium ion, the [K ] will equal the [HC H O ], so +
4 4 6
−

determining the concentration of the hydrogen tartrate ion HC H O by titration with a base will 4 4 6
−

allow us to determine the K . The analytical reaction to achieve that is

sp

HC H O (aq) + OH (aq) →  C H O (aq) + H O (l)

4 4 6
− −
4 4 6
2−
2 (3)

To illustrate the difference between the solubility and the solubility product constant, we

will analyze two different saturated solutions of potassium hydrogen tartrate, one without added

potassium ion, and one with potassium ion added in the form of KCl, a very soluble salt, in

addition to the potassium hydrogen tartrate. In both cases, the value of the Ksp is given by:
 K = [K+ ]tot [HC4H4O6 − ] (4)
sp

where the subscript on the symbol [K+ ]tot is just a reminder that it is the total potassium ion

concentration that matters. But [K+ ]tot will be different in the two saturated solutions:

In both cases the concentration of hydrogen tartrate ion is determined by titration. The

calculated values of the Ksp should be the same in each case, but the lower solubility of

potassium hydrogen tartrate in the second solution, due to the common ion effect of added KCl,

will result in a lower concentration [HC4H4O6−] found in the titration.

Making that comparison introduces another minor complication, the fact that chemical

processes involving ions in solution can be affected merely by the presence of other charged

species, whether or not they are directly involved in that process. The effect is related to the

activities of the species, sometimes described as “effective concentrations”. Ions moving in an

environment of other charged species with which they can interact behave slightly differently

than when those other charges are absent. To make a fair comparison between the two different

saturated solutions we will make sure that the one without extra potassium ions does at least have

the same number of charged particles present, to keep the ionic environments more uniform.

PROCEDURE:
NOTE: The procedure as written has midshipmen working in pairs, with each pair working on the same saturated solution. Pairs

would then exchange data with students using the other saturated solution. Your Instructor may prefer a different arrangement. Follow

the guidance of your Instructor.

Titration of Saturated Potassium Hydrogen Tartrate Solution

1. Two midshipmen working together will need about 100 mL (total) of the appropriate

saturated solution.Obtain about 100 mL of your assigned saturated solution of

 KHC4H4O6 (Solution I or Solution II) in a clean, dry 100 mL beaker. Identify (circle)

your assigned saturated solution on the Data page.

2. The saturated solution must be filtered before use; one filter set-up per pair of

midshipmen is sufficient. Create a filter paper cone by folding a circle of filter paper in

half, and then that semicircle in half again. Open the cone with three plies to one side and

one on the other and insert it into a glass filter funnel. Set the funnel in a filter funnel

rack, with a clean, dry 100 mL beaker below the spout.

3. Pour a small amount of the saturated solution into the filter paper cone, wetting it down

to the glass funnel.Then continue to pour the solution through the filter, collecting the

effluent. Use the filtered solution ONLY for all subsequent steps; there should be plenty

for both midshipmen working together.

4. Rinse your 25 mL pipet with the filtered solution. (To rinse a pipet, draw up a small

amount of liquid into the pipet and then manipulate the glassware so that the solution

contacts all surfaces. Discard the rinse.)

5. Use a clean, dry 100 mL beaker to obtain ~ 100 mL of the standard NaOH solution.

Record the concentration of the NaOH solution on the Data page. Label the beaker so it

can be replenished if necessary without contamination of reagent.

6. Each midshipman in the pair should perform the following steps, so that each

midshipman analyzes at least one sample of the saturated solution. There is sufficient

equipment that each partner can do these steps at the same time. Record your data in the

separate Trial 1 and Trial 2 columns for the appropriate saturated solution.

1. Using your rinsed pipet, transfer 25.00 mL of the filtered saturated solution into a

125 mL Erlenmeyer flask. Add about 20 mL of deionized water and 2 drops of

 phenolphthalein indicator solution. This is the sample of saturated potassium

hydrogen tartrate you will analyze.

2. Use a small amount (~ 5 mL) of the NaOH solution to rinse your buret, coating all

surfaces and discarding the rinse. Fill up the buret with the remaining NaOH

solution and place it on a ring stand, using a buret clamp.

3. Set up the buret, ring stand and Erlenmeyer flask of sample. Place a piece of

white paper under the Erlenmeyer flask.

4. Record the initial volume reading of the buret on the Data page. (Read the buret to

two decimal places.)

5. Titrate the solution to the phenolphthalein end point, stirring or swirling as you go

to ensure mixing. The end point is the first faint pink color that persists for at least

30 seconds. Record the final buret reading (to two decimal places) on the Data

pages.

7. If the volumes of NaOH used for trials 1 and 2 do not agree within 1 mL, repeat step 6 (a-e)

for a third trial.If you have good agreement, you may skip the third trial.

8.Obtain data from classmates assigned to work with the other saturated solution of KHC4H4O6

(either Solution I or Solution II). Solution II data includes the concentration of KCl; be sure

to record that as well. You need all data for two trials of each solution to do the analysis.

Clean-up

1. Empty all solutions down the drain, with flowing water. Discard any filter paper cones in

the trash.

2. Clean, and then rinse all glassware with distilled water. Return materials to their original

locations.
 SOLUBILITY AND THE SOLUBILITY PRODUCT CONSTANT

DATA
           

DATA ANALYSIS

1. For each titration of each saturated solution, calculate the number of moles of OH used
−

to reach the end point of the titration.  Show your work for one of the trials for both Solution I

and Solution II, and report the result for a second trial of each solution.  (If you did three trials,

only analyze the two that most closely agree.)

2. Using the stoichiometry of the titration reaction (reaction (3), p. E44-2) and the volume

of the sample solution, calculate the molar concentration of HC4H4O6− for each titration of each

saturated solution.  Show your work for one of the trials for both Solution I and Solution II, and

report the result for a second trial of each solution. (If you did three trials, only analyze the two

that most closely agree.)

3. Knowing the [HC4H4O6−] in each solution, and the [KCl] provided in saturated solution

II, use the table on p. E44-2 to find the total potassium ion concentration [K+]tot for each trial.

Show your work for one of the trials for both Solution I and Solution II, and report the result for

a second trial of each solution. (If you did three trials, only analyze the two that most closely

agree.)
4. Use the measured [HC4H4O6−] (question 2) and the calculated [K+]tot (question 3) for

each trial, calculate the Ksp for potassium hydrogen tartrate, KHC4H4O6. Average the values

obtained for the two trials of Solution I. Then average the values obtained for the two trials of

Solution II. Show your work for one of the trials for both Solution I and Solution II, and report

the result for a second trial of each solution. (If you did three trials, only analyze the two that

most closely agree.

5. Based on the measured [HC4H4O6−] (question 2) and the molar mass of KHC4H4O6,

what is the gram solubility of KHC4H4O6 in each of the solutions? Average the values obtained

for the two trials of Solution I. Then average the values obtained for the two trials of Solution II.

Show your work for one of the trials for both Solution I and Solution II, and report the result for
a second trial of each solution. (If you did three trials, only analyze the two that most closely

agree.)

Post-Lab Questions

1. Compare the values of Ksp determined for Solution I (without added KCl) and Solution II

(with added KCl). Should they be the same, or different? Why? – Explain your answer.

2. Compare the values of the solubility determined for Solution I (without added KCl) and

Solution II (with added KCl). Should they be the same, or different? Why? – Explain your

answer.

3. At room temperature, the maximum solubility of KCl is 3.74 M, well above the KCl content

of Solution II used in the experiment. Use the value of Ksp = 1.1 x 10-3 for KHC4H4O6 and

calculate what the solubility of KHC4H4O6 would be in a solution which was also 3.74 M in

KCl. Set up the I.C.E. table and show your work.

 References and Supplementary Materials

Books and Journals

Chang,Raymond;2010;Chemistry 10th edition;New York, NY USA; McGrawHill.

Zumdahl, Steven S. and Susan A. Zumdahl. 2007. Chemistry 7th edition. Boston/New

York. Houghton Mifflin Company

Online Supplementary Reading Materials

pH Curves (Titration Curves);

http://www.chemguide.co.uk/physical/acidbaseeqia/phcurves.html; Apr 25, 2017

Bronsted Acids and Bases; https://www.boundless.com/chemistry/textbooks/boundless-

chemistrytextbook/aqueous-reactions-4/acid-base-reactions-47/bronsted-acids-andbases-

242-8358/;

Acid Ionization Constants at 25°C;

http://bilbo.chm.uri.edu/CHM112/tables/KaTable.htm; Apr 25, 2017

The Common Ion Effect; https://www.boundless.com/chemistry/textbooks/boundless-

chemistrytextbook/acid-base-equilibria-16/homogeneous-versus-heterogeneoussolution-

equilibria-116/the-common-ion-effect-473-3639/; Apr 25, 2017

Acids and Bases;

https://www.khanacademy.org/science/chemistry/acidsand-bases-topic;

Acids and Bases | Chemistry | Visionlearning;

http://www.visionlearning.com/en/library/Chemistry/1/Acids-andBases/58;

Online Instructional Videos

Arrhenius definition of acids and bases; https://youtu.be/Y4HzGldIAss;

Brønsted-Lowry definition of acids and bases;https://youtu.be/XVOU9c3crbc;

Autoionization of water;https://youtu.be/NUyYlRxMtcs;

Strong acids and strong bases; https://youtu.be/gsu4gjrFApA;

Acid-base properties of salts;https://youtu.be/HwkEQfsJenk;

Acid-Base Reactions in Solution;https://youtu.be/ANi709MYnWg?list=

PL8dPuuaLjXtPHzzYuWy6fYEaX9mQ Q8oGr;

Water and Solutions;https://www.youtube.com/watch?v=

AN4KifV12DA&list=PL8dPuuaLjXtPHzz YuWy6fYEaX9mQQ8oGr&index=7;

pH and POH;https://www.youtube.com/watch?v=

LS67vS10O5Y&list=PL8dPuuaLjXtPHzz YuWy6fYEaX9mQQ8oGr&index=30;

pH value: Why is soil important to farmers?;https://www.youtube.com/watch?v=

zQowljL8e5E&index=16&list=PLRSIe0 MUxDncRjJ2vYvsXDU0pDnKObrAD;

Solubility – Why does soda fizz when you shake it?;

https://www.youtube.com/watch?

v=sinqcBoqkEE&index=15&list=PLRSIe0MUxDncRjJ2vYvsXDU0pDnKObrAD;