Department of Chemical Engineering

ELA 301

University of Benin

I
TITLE PAGE
Title of Experiment: HEAT OF SOLUTION
Aim of the Experiment: TO DETERMINE THE HEAT OF SOLUTION OF
BENZOIC ACID

Date of the Experiment: 28/03/2023

Experiment Number: 04
Name of Student: MORDI FAVOUR GOD’SPOWER
Matriculation Number: ENG1905016
Serial Number: 50
Group: A6
Level: 300
Course Code: ELA 301
Name of Instructor: ENGR. W. O. OWABOR

TABLE OF CONTENTS
II
TITLE PAGE.................................................................................................................II
TABLE OF CONTENTS................................................................................................III
List of Figures and Tables.........................................................................................IV
List of figures........................................................................................................IV
List of Tables.........................................................................................................IV
ABSTRACT..................................................................................................................V
INTRODUCTION.........................................................................................................1
THEORY......................................................................................................................8
DESCRIPTION OF APPARATUS.................................................................................10
PROCEDURE.............................................................................................................14
RESULTS AND CALCULATIONS.................................................................................15
DISCUSSION.............................................................................................................19
SAFETY PRECAUTIONS TAKEN.................................................................................20
CONCLUSION...........................................................................................................21
RECOMMENDATIONS..............................................................................................21
REFERENCES............................................................................................................22
APPENDIX A: Sample Calculation............................................................................23
APPENDIX B: Nomenclature....................................................................................24

List of Figures and Tables

List of figures
Figure 1: Beaker.......................................................................................................10
III
Figure 2: Conical flask..............................................................................................11
Figure 3: Seperating funnel.....................................................................................11
Figure 4: Burette......................................................................................................11
Figure 5: Funnel.......................................................................................................12
Figure 6: Retort Stand.............................................................................................12
Figure 7: Measuring Cylinder..................................................................................12
Figure 8: Pipette......................................................................................................12
Figure 9: Thermometer...........................................................................................13
Figure 10: Graph of Log Ca against 1/T...................................................................16

List of Tables
Table 1: Titration at 34oc (T1)...................................................................................15
Table 2: Titration at 56oC (T2)..................................................................................15
Table 3: Table for the graph....................................................................................15

ABSTRACT
This experiment was done in order to determine the solubility of the benzoic acid over a
range of temperatures and consequently calculate its heat of solution. The experiment was

IV
conducted by using a solution of saturated benzoic acid together with the titration method
using 0.1M NaOH solution and phenolphthalein indicator. This operation was performed at 34
0
C and 56 0C; and was done by heating the solution contained in the 250ml conical flask and
conducting the titration upon equilibrium. Variables such as temperatures, initial and final mass
as well as the initial and final volumes of the solution before and after titration, giving rise to
the calculation of the solubility of the benzoic acid as well as the enthalpy of dissolution.

Results show that there is a linear relationship between solubility and temperature. The
solubility of benzoic acid increases as the temperature increase. The heat of solution, ∆𝐻, was
determined by using the van’t Hoff equation, with solubilities known at two different
temperatures. The heat of solution was found to be – 8144.40kJ/mol. Since the ∆𝐻 has a
negative value, indicating that the dissolution of benzoic acid is an exothermic process. The
energy of hydration is much smaller than the energies associated with the breakage of bonds of
water molecules and benzoic acid molecules.

V
INTRODUCTION
The heat of solution, also called enthalpy of dissolution, or enthalpy of solution is the
enthalpy change associated with the dissolution of a substance in a solvent at constant
pressure resulting in infinite dilution. The enthalpy of solution is one of the three dimensions of
solubility analysis. Solubility is the amount of a particular substance that can dissolve in a
particular solvent; it is usually given in mol/L. A solvent is a species capable of dissolving other
substances (solutes), while a solute is the dissolved matter in a solution, or the component of a
solution that changes its state.

For a given solute, the heat of solution is the change in energy that occurs as one mole
of the solute dissolves in a solvent. During the dissolving process, solutes either absorb or
release energy.

If solutes absorb energy from the solvent as they dissolve, the solution gets colder and
the reaction is endothermic. If solutes release energy to the solvent as they dissolve, the
solution gets warmer and the reaction is exothermic. By using a titration method to determine
the solubility and measuring the change in the temperature of the solution during the
dissolving process, the heat of solution can be calculated.

Solutions are very common in nature. In order for any reaction to occur there must be a
change in energy. The ease of dissolution is dependent on the temperature of the system and
type of solution, being endothermic or exothermic. Generally, when dissolution occurs, the
entropy of the system increases. It is important to determine the heat of solution (enthalpy
change); this is because a change in enthalpy takes account of energy transferred to the
environment through the expansion of the system under study.

The total enthalpy, H, of a system cannot be measured directly. Thus, change in

enthalpy (∆𝐻), is a more useful quantity than its absolute value. The change, ∆𝐻, is positive in
endothermic reactions, and negative in exothermic processes. Enthalpy is a thermodynamic
potential. It is a state function and an extensive quantity. The enthalpy is the preferred
expression of system energy changes in many chemical, biological, and physical measurements,
because it simplifies certain descriptions of energy transfer.

ENTHALPY:

Enthalpy is a thermodynamic quantity that describes the total heat content of a system,
including the heat content that results from the internal energy of the system and the energy

1
required to maintain the system's pressure and volume. It is represented by the symbol H and is
often measured in units of joules or calories.

In a closed system, the change in enthalpy is equal to the heat gained or lost by the system
during a process that occurs at constant pressure. Mathematically, the change in enthalpy can
be represented by the equation:

ΔH = H₂ - H₁

where ΔH is the change in enthalpy, H₁ is the enthalpy of the initial state, and H₂ is the enthalpy
of the final state.

Enthalpy is a useful thermodynamic quantity because it takes into account the pressure-volume
work that occurs during a process, which is often important in chemical reactions and other
thermodynamic processes. For example, when a gas is compressed, work is done on the gas,
which increases its internal energy and, thus, its enthalpy.

Enthalpy is also useful in determining the heat of reaction for chemical reactions. The heat of
reaction is the amount of heat that is released or absorbed during a chemical reaction. This
quantity is related to the change in enthalpy for the reaction and can be determined
experimentally by measuring the heat released or absorbed during the reaction.

In summary, enthalpy is a thermodynamic quantity that describes the total heat content of a
system, including both the internal energy of the system and the energy required to maintain
the system's pressure and volume. It is an important concept in thermodynamics and is often
used to calculate the heat of reaction for chemical reactions.

SOLUTION:

A solution is a homogeneous mixture of two or more substances, where the different

components are evenly distributed throughout the mixture. The substance that is present in
the greatest amount is called the solvent, while the other substances that are present in smaller
amounts are called solutes.

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There are many different types of solutions, but the most common type is a liquid solution,
where a solid, liquid or gas is dissolved in a liquid solvent. For example, salt dissolved in water is
a common liquid solution. Another common type of solution is a gas solution, where a gas is
dissolved in a liquid or another gas. An example of a gas solution is carbon dioxide dissolved in
water, which creates carbonated water.

Solutions can also be classified based on their concentration. The concentration of a solution is
the amount of solute present in a given amount of solvent or solution. There are different ways
to express the concentration of a solution, such as percent concentration, molarity, molality,
and normality.

Percent concentration is the most common way to express the concentration of a solution. It is
usually expressed as the mass of solute present in a given mass or volume of solution, and is
represented as a percentage. For example, a solution with 5% sodium chloride means that 5
grams of sodium chloride are present in 100 ml of solution.

Molarity is another way to express the concentration of a solution. It is defined as the number
of moles of solute per litre of solution. For example, a solution with a molarity of 0.1 M means
that there are 0.1 moles of solute per litre of solution.

Molality is similar to molarity, but is defined as the number of moles of solute per kilogram of
solvent. This is important for some chemical reactions, where the solvent can also play a role in
the reaction.

Normality is another way to express the concentration of a solution, but is used less frequently
than the other methods. It is defined as the number of equivalents of solute per liter of
solution. Equivalents are used for reactions that involve acids or bases, where one equivalent is
the amount of acid or base that can donate or accept one mole of hydrogen ions.

In conclusion, a solution is a homogeneous mixture of two or more substances, where the

substance present in the greatest amount is called the solvent and the other substances
present are called solutes. Solutions can be classified based on their concentration, which can

3
be expressed as percent concentration, molarity, molality, or normality. Understanding the
properties and behavior of solutions is important in many areas of chemistry, including
chemical reactions, analytical chemistry, and materials science.

TYPES OF SOLUTIONS:

The substance that is present in the largest amount in a solution is called the solvent, and the
substance that is present in smaller amounts is called the solute. The types of solutions in
chemistry can be classified based on the nature of the solute and the solvent. Here are the
common types of solutions in chemistry:

Solid Solutions:

Solid solutions are homogeneous mixtures of two or more solids. In solid solutions, the solute is
distributed uniformly in the solvent. An example of a solid solution is an alloy, which is a
mixture of two or more metals. An example of an alloy is brass, which is a mixture of copper
and zinc.

Liquid Solutions:

Liquid solutions are homogeneous mixtures of two or more liquids. An example of a liquid
solution is an alcohol-water mixture. When ethanol is mixed with water, a homogeneous
solution is formed.

Gas Solutions:

Gas solutions are homogeneous mixtures of two or more gases. An example of a gas solution is
air, which is a mixture of gases like nitrogen, oxygen, carbon dioxide, and others.

Supersaturated Solutions:

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Supersaturated solutions are solutions that contain more solute than the solvent can dissolve at
a particular temperature. These solutions are unstable and can crystallize out the excess solute
if disturbed. For example, if sugar is added to water until it cannot dissolve anymore at room
temperature, the solution will become supersaturated. If disturbed, the excess sugar will
crystallize out.

Saturated Solutions:

Saturated solutions are solutions that contain the maximum amount of solute that the solvent
can dissolve at a particular temperature. At this point, any additional solute added will not
dissolve, and a precipitate may form. An example of a saturated solution is a solution of table
salt in water.

Unsaturated Solutions:

Unsaturated solutions are solutions that can dissolve more solute at a particular temperature.
These solutions are not at their maximum capacity for solute dissolution. An example of an
unsaturated solution is a solution of sugar in water that can still dissolve more sugar.

In conclusion, the type of solution depends on the nature of the solute and the solvent, and it is
important to understand the different types of solutions to conduct experiments and solve
chemical problems effectively.

Heat of Solution occurs when a solute dissolves in a solvent and the heat change can either be
EXOTHERMIC OR ENDOTHERMIC.

Exothermic and endothermic reactions are two types of chemical reactions that describe the
transfer of heat energy that occurs during a chemical reaction.

Chemical reactions involve the breaking and formation of chemical bonds between atoms,
which requires the transfer of energy. This energy can be in the form of heat, light, or
electricity. Exothermic and endothermic reactions describe the direction of the transfer of heat
energy during a chemical reaction.

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EXOTHERMIC REACTION:

An exothermic reaction is a reaction that releases heat energy to its surroundings. In an

exothermic reaction, the energy released by the reaction is greater than the energy required to
break the bonds of the reactants, resulting in a net release of energy.

Exothermic reactions are those that release heat energy to the surroundings. This can be
observed in the form of heat, light, or a combination of both. During an exothermic reaction,
the energy required to break the chemical bonds of the reactants is less than the energy
released by the formation of new bonds in the products.

The excess energy is released into the surrounding environment. The classic example of an
exothermic reaction is combustion, which is the reaction between a fuel and oxygen.

Other examples of exothermic reactions include combustion reactions, such as burning wood or
fuel, and the reaction between an acid and a base.

This reaction produces heat and light, as well as the products of water and carbon dioxide.

ENDOTHERMIC REACTION:

On the other hand, an endothermic reaction is a reaction that absorbs heat energy from its
surroundings. In an endothermic reaction, the energy required to break the bonds of the
reactants is greater than the energy released by the reaction, resulting in a net absorption of
energy.

The energy required for the reaction is supplied from the surrounding environment, resulting in
a decrease in temperature in the surroundings.

A classic example of an endothermic reaction is the melting of ice. When ice melts, heat energy
from the surroundings is absorbed to break the bonds between the water molecules, resulting
in a temperature decrease in the surroundings

Other examples of endothermic reactions include the reaction between baking soda and
vinegar, and the reaction between ammonium nitrate and water.

6
The heat of solution has several practical applications in various fields, including chemistry,
biology, and materials science. Some of its important applications are:

Solubility: The heat of solution plays a crucial role in determining the solubility of a solute in a
particular solvent. If the heat of solution is positive, it means that the solute is less soluble in
the solvent at higher temperatures. In contrast, a negative heat of solution indicates that the
solute is more soluble at higher temperatures.

Pharmaceutical industry: The heat of solution is essential in the development of

pharmaceutical formulations, including the solubility of drugs in various solvents. A better
understanding of the heat of solution can help in optimizing drug delivery systems and
enhancing drug efficacy.

Energy storage: The heat of solution can be used in the development of new energy storage
systems, such as batteries and fuel cells. By measuring the heat of solution, it is possible to
design more efficient and cost-effective energy storage systems.

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THEORY
The heat of solution or enthalpy of solution is one of the three dimensions of solubility
analysis. It is the change in enthalpy associated with the dissolution of a solvent at constant
pressure resulting in infinite dilution, thus as one mole of the solute dissolves in the solvent. In
the process, energy can either be absorbed or released; it is expressed in kJ/mol at constant
temperature, with positive values indicating endothermic values and negative values indicating
energy released or exothermic energy. Dissolving a gas in liquid solvent releases energy, as
heat, into the surroundings in an exothermic reaction. The temperature of the solution
decreases as energy leaves the system; therefore, solubility of a gas increases with a decrease
in temperature of solution. On the other hand, when the solution is heated, the reverse
reaction occurs and gas evolves. Enthalpy of hydration is one of the most common types of
heat of solution. A substance, commonly a salt is dissolved in water. When completely
dissolved, the heat of solution is at its maximum. Dissolution of a solute can occur in three
steps:

a. Breaking of solute-solute attraction (endothermic)

b. Breaking of solvent-solvent attractions (endothermic)
c. Forming solvent-solute bonds (exothermic)

The sum of the individual enthalpy changes of each step is the overall value of the
enthalpy change. Stronger bonds are formed in solutions with negative enthalpy changes and
these solutions tend to have a lower vapor pressure. A positive enthalpy indicates that the
solute is not easily dissolved in the solvent1 ; while a negative enthalpy indicates that a solute is
easily dissolved in the solvent.

Three conditions are fulfilled in the process, as mentioned before, the pressure remains
constant, the temperature remains constant (indicating standard conditions of temperature
and pressure)2 , and there is expansion against the atmosphere and work is done. The enthalpy
of solution is only valid for dissolution of a pure substance into another pure substance.
Enthalpies of solution of most substances can be measured directly when the resulting solution
is liquid. A constant temperature can be maintained if the solute is dissolved slowly.

1. More on this in the discussion section

2. Details of Van’t Hoff equation for standard and thermodynamic conditions in Appendix A

8
 When a solid is dissolved in a solvent in which it is soluble, it dissolves until saturation is
reached at a certain temperature. It is necessary to determine the amount of solute dissolved
and the nature of solid phase in equilibrium with the solution when performing solubility
measurements. Solubility depends on temperature; it increases with temperature in an
endothermic reaction3 and decreasing with increase in temperature in exothermic reactions.
The well-known van't Hoff equation relates the solubility of a reaction, K, to the enthalpy
change of that reaction, ∆𝐻 :
d lnx −∆ H
=
dT RT 2

Integrating the equation gives4 :

ln ( xx 21 )= −∆R H ( T12 − T11 )

Where x1 is solubility at T1 and x2 is solubility at T2.

3. This is the case in this experiment. More in the discussion section on page 16
4. See Appendix A for the integration steps

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DESCRIPTION OF APPARATUS
 Beaker
 Conical Flask
 Separating Funnel
 Burette
 Funnel
 Retort Stand
 Measuring Cylinder
 Timer
 25ml Pipette
 Thermostat
 Heater
 Thermometer

The chemicals used to for the experimental work were: solid benzoic acid, sodium
hydroxide pellets, phenolphthalein indicator and water.

 Beaker: A beaker is a cylindrical container used to store, mix and heat liquids in
laboratories. Most are made of glass, but other non-corrosive materials, such as
metal and heatresistant plastic, are also used. Beakers usually have a flat bottoms
and a lip around the top.

Figure 1: Beaker

 Conical Flask: An Erlenmeyer flask, also known as a conical flask (BrE) or a titration
flask, is a type of laboratory flask which features a flat bottom, a conical body, and a
cylindrical neck. Flasks can be used for making solutions or for holding, containing,
collecting, or sometimes volumetrically measuring chemicals, samples, solutions,
etc.

10
 Figure 2: Conical flask

 Separating Funnel: A separating funnel, also known as a separation funnel,

separating funnel, or colloquially sep funnel, is a piece of laboratory glassware used
in liquid-liquid extractions to separate the components of a mixture into two
immiscible solvent phases of different densities.

Figure 3: Seperating funnel

 Burette: A burette is a graduated glass tube with a tap at one end, for delivering
known volumes of a liquid, especially in titrations. It is a long, graduated glass tube,
with a stopcock at its lower end and a tapered capillary tube at the stopcock's
outlet.

Figure 4: Burette

 Funnel: Funnels are apparatuses that have been made for use in the chemical
laboratory. It is used to channel liquid or fine-grained substances into containers
with a small opening.

11
 Figure 5: Funnel

 Retort Stand: A retort stand, sometimes called a clamp stand or a ring stand, is a
piece of scientific equipment to which clamps can be attached to hold other pieces
of equipment and glassware – for instance, burettes, test tubes and flasks.

Figure 6: Retort Stand

 Measuring Cylinder: A measuring cylinder, graduated cylinder or mixing cylinder is a

common piece of laboratory equipment used to measure the volume of a liquid. It
has a narrow cylindrical shape. Each marked line on the graduated cylinder
represents the amount of liquid that has been measured.

Figure 7: Measuring Cylinder

 Pipette: A pipette (sometimes spelled pipet) is a laboratory tool commonly used in

chemistry, biology and medicine to transport a measured volume of liquid, often as
a media dispenser. Pipettes come in several designs for various purposes with
differing levels of accuracy and precision, from single piece glass pipettes to more
complex adjustable or electronic pipettes.

Figure 8: Pipette

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 Thermostat: A thermostat is a device which keeps a constant temperature. It is built
with an electric heater and two thermometers, the contact thermometer and the
laboratory thermometer.
 Heater: A heater is a device used for heating solutions. Unlike a thermostat, a heater
would continuously raise the temperature of a solution without limit.
 Thermometer: A thermometer is a device that measures temperature or a
temperature gradient (the degree of hotness or coldness of an object). A
thermometer has two important elements: (1) a temperature sensor (e.g. the bulb
of a mercury-in-glass thermometer) in which some change occurs with a change in
temperature; and (2) some means of converting this change into a numerical value
(e.g. the visible scale that is marked on a mercury-in-glass thermometer or the
digital readout on an infrared model).

Figure 9: Thermometer

13
PROCEDURE
The experiment was conducted under two different conditions, the first being at room
temperature, the second being at 56°C

At Room Temperature:

Using a weighing balance, 2g of benzoic acid was measured and transferred into a beaker using
a spoon.

Using a measuring cylinder, 200ml of distilled water at room temperature was transferred into
a beaker containing 2g of benzoic acid to form a saturated Solution.

This solution was stirred for about 30 seconds to ensure an even mixture.

At thermometer was placed in the solution to measure this room temperature as 34°C.

Using a pipette, 25ml of this solution was each transferred into two separate conical flasks for
two titre values at this temperature.

Using a funnel, 0.1M solution of NaOH was transferred into a burette. Noting the initial and
final volume of NaOH (at endpoint), this was separately titrated against each content conical
flask of which two drops of phenolphthalein was added.

The end point was seen when the content of the conical flask changed from colourless to pink.
From this the volume of NaOH used in the titration was obtained by subtracting its initial
volume from the final volume.

At above Room Temperature (56°C):

The initial saturated solution was discarded. Using a weighing balance, 2g of benzoic acid was
measured and transferred into a beaker using a spoon.

Using a measuring cylinder, 200ml of distilled water at room temperature was transferred into
a beaker containing 2g of benzoic acid to form a saturated Solution.

This solution was stirred for about 30 seconds to ensure an even mixture.

We put the solution in a bowl of water and set it on a gas cylinder to boil.

A thermometer was used to check to ensure the content of the conical flask was up to 56°C
before titration was done. One at a time, just as done at room temperature, each content of
the conical flask was titrated with the NaOH in the burette and two titre values were obtained.

14
RESULTS AND CALCULATIONS
The dissolution of benzoic acid is given by the following chemical equation:
𝐶6𝐻5𝐶𝑂2𝐻 ⇋ 𝐻 + + 𝐶6𝐻5𝐶𝑂2 –
And the reaction of benzoic acid and sodium hydroxide is given by the following chemical
equation:
𝐶6𝐻5𝐶𝑂2𝐻 + 𝑁𝑎𝑂𝐻 ⇋ 𝐶6𝐻5𝐶𝑂2𝑁𝑎 + 𝐻2O

1st TITRATION (ml) 2nd TITRATION (ml)

FINAL READING 11.00 21.60
INITIAL READING 0.00 11.00
FINAL – INITIAL 11.00 10.60
Table 1: Titration at 34oc (T1)

11.00+10.60
Average titre value of base = = 10.8
2

1st TITRATION (ml) 2nd TITRATION (ml)

FINAL READING 8.60 17.40
INITIAL READING 0.00 8.60
FINAL – INITIAL 8.60 8.80
Table 2: Titration at 56oC (T2)

8.60+8.80
Average titre value of base = = 8.70ml
2

1
CA (M) T(K) Log (CA)
T (K )
0.0432M 307.15 -1.3645 0.0032557
0.0348M 329.15 -1.4584 0.0030381
Table 3: Table for the graph

T (OC) to K = Value in oC + 273.15

15
 -1.3
0.003 0.0031 0.0032 0.0033
-1.32

-1.34

-1.36

-1.38 Y-Values
-1.4 Linear (Y-Values)

-1.42

-1.44

-1.46

-1.48
slope = 431.5257
Figure 10: Graph of Log Ca against 1/T

CALCULATIONS
THE EQUATION FOR THE REACTION OF SODIUM HYDROXIDE AND BENZIOC ACID IS AS
FOLLOWS;
C 6 H 5 COOH + NaOH → C6 H 5 COONa + H 2 O

CAVA NA
USING THE FORMULA =
CBVB NB

Where, CA = Concentration of benzoic acid = ?

CB = concentration of base (NaOH) = 0.1M

VA = Volume of acid + water solution used = 25ml

VB = volume of base used = our average titre value

NA = number of moles of Benzoic acid used in the stoichiometric equation = 1

NB = number of moles of NaOH used in the stoichiometric equation = 1

MAKING CA THE SUBJECT OF THE FORMULA ABOVE WE GET;

CB∗VB∗NA
CA =
VA∗NB

CA at 34oc (room temperature)

16
 0.1∗10.8∗1
CA = = 0.0432M
25∗1

CA at 56oc

0.1∗8.70∗1
CA = = 0.0348M
25∗1

FINDING ΔH FROM OUR GRAPH

From our graph we can see that our Slope = 431.5257

Using the formula

− ΔH
Slope =
2.303 R

We can find our heat of solution ΔH by making it the subject of formula

ΔH = -Slope*2.303*R

Where R = 8.3145Jmol-1K-1

ΔH = -431.5257*2.303*8.3145

So, ΔH = -8262.98 Jmol-1K-1

USING VAN’T HOFF EQUATION TO FIND ΔH

( )
x1 −∆ H 1 1
ln = −
x2 R T2 T 1

Where, R = Ideal Gas Constant

ΔH = Enthalpy (Heat) Change of Solution
T = absolute temperature
x = Solubility of solute in solvent

Finding number of moles (n) of solute

Number of moles (n) = CAVA

CA = average value concentration of acid at 34ocand also at 56oc

VA = Volume of acid used

17
TO FIND X1 AND X2

We have to find (n) at temperatures 27oc and 50oc and call it n1

So, n1 = 0.0432*25 = 1.08mol

n2 = 0.0348*25 = 0.8725mol

n1 1.08
X1 = = = 0.5531`
n 1+ n 2 1.08+0.8725

n2 0.8725
X2 = = = 0.4469
n 1+ n 2 1.08+0.8725

T1 =307.15

T2 =329.15

APPLYING VAN’T HOFF EQUATION

( )
x1 −∆ H 1 1
ln = −
x2 R T2 T 1

ln
0.5531 −∆ H
=
1
( −
1
0.4469 8.314 329.15 307.15 )
8.314 ln(1.2376)
−∆ H =
( 1
−
1
329.15 307.15 )
∆ H =−8144.40Jmol-1K-1

18
DISCUSSION
The heat of solution of benzoic acid was found to be negative at−8144.40 Jmol-1K-1. This is an
indication that the dissolution of benzoic acid in water for this experiment is exothermic. Being
exothermic, the solubility of benzoic acid in water decreases with increase in temperature. This
is evident in the result.

Basically, solubility increases with temperature in an endothermic reaction. It is the case for
most of the solvents. The situation is though different for gases. With increase in temperature,
they became less soluble in each other and in water, but more soluble in organic solvents. The
heat of solution being a positive value is also an indication that benzoic acid is not easily
dissolved in water, and needs other factors to be in place to aid in the dissolution (in this case,
temperature).

The experiment was carried out to determine the heat of solution (ΔH sol) of benzoic acid in
water from solubility measurements.

To obtain the above said, titration was carried out with NaOH in a burette against 25ml
saturated solution of benzoic acid at room temperature (25°C), at temperature 50°C and 25ml
of the solution at 65°C separately using phenolphthalein indicator.

The volumes of NaOH used at end point (when the solution in the conical flask turned from
colourless to pink) at room temperature (25°C), 50°C and 65°C were averagely 6.80ml, 3.9ml
and 5.0ml respectively.

CA V A N A
Subsequently, using the stoichiometric equation of the titration and the formula =
CB V B N B

the concentrations of benzoic acid (C A) at room temperature, at 50°C and at 65°C was
calculated as 0.0272M, 0.0156M and 0.02M respectively.

From these concentrations, the number of moles (n) was calculated to be 0.535mol and
0.445mol, the solubilities of the solute X 1 and X2was calculated using the number of moles
gotten and at average value of temperatures between 27 oc and 50oc and between 50oc and
65oc.

( )
x1 −∆ H 1 1
From these solubility values, and using Van’t Hoff Isochore equation ln = −
x2 R T2 T 1

19
The heat of solution, ΔHsol = -8144.40 Jmol-1K-1
And from our graph, ΔHsol= -8262.98 Jmol-1K-1

Possible sources of error in this experiment include heat loss to the surroundings, incomplete
mixing of the solutions, and inaccuracies in the temperature measurement. Also the day of the
experiment was a very sunny day, affecting the room temperature. A gas cylinder was also used
in place of a thermostat. These errors can be minimized by ensuring that the experiment is
conducted in a thermally insulated environment, using a powerful stirrer to ensure complete
mixing, and using a precise thermometer.

SAFETY PRECAUTIONS TAKEN

 Care was taken to avoid spilling any of the chemical compounds on the skin.
 Care was taken to avoid parallax error when taking the readings on the measuring
cylinder.
 Care was taken not to draw up solid particles when pipetting the heated benzoic acid
solution.
 While taking the readings on the burette, the lower meniscus was read to ensure
accurate measurements.
 Laboratory coats were worn at all times while the experiment was taking place to avoid
spilling any chemical on the skin.
 A warm pipette was used to avoid crystallization of the acid in a cold pipette.
 During the draining, the funnel was opened bit by bit in order to ensure that pressure
did not build up in the funnel.
 In the second test, the titration was done with care to ensure it was done in drop wise in
order to avoid exceeding the endpoint since just a small amount of the iodine was left in
the hexane phase.

20
CONCLUSION
The heat of solution, ΔH, was found to be -8144.40kJ/mol. Since ΔH has a negative value, it
indicates that the dissolution of benzoic acid is an exothermic process. The energy of hydration
is much smaller than the energies associated with the breakage of bonds of water molecules
and benzoic acid molecules.

RECOMMENDATIONS
These are my recommendations for future experiments having the same aim to achieve
accuracy and save time;

 The experiment should be carried out over a wider range of temperatures and the heat
of solution derived from the slope of the plot of ln(K) versus 1/T and the results
compared with that gotten from the van’t Hoff equation.
 It should be announced prior to the experiment that students should browse deeply
about the topic so that the instructor would nor spend a lot of time explaining. This
would save time and give the students enough time to carry out the experiment
accurately.
 The experiment should be attempted at lower temperatures of the solution, as this
would reduce the time to heat the solution.

21
REFERENCES
1. Bookrags. (2006). Heat of Solution. Retrieved August 16, 2011, from BookRags:
http://www.bookrags.com/research/heat-of-solution-woc
2. Department of Chemical Engineering. (2011). Practical Manual S4. Durban, KZN,
South
3. Africa: Durban University of Technology. M, S. J., Ness, H. V., & Abbott, M.
(2003). Introduction to Chemical Engineering
4. Thermodynamics. In J. Smith, H. V. Ness, & M. Abbott, Introduction to Chemical
Engineering Thermodynamics (pp. 426 - 432). New York: McGraw - Hill.
5. University, A. (2005). heat of solution. Retrieved August 14, 2011, from
http://www.pulse.pharmacy.arizona.edu/resources/heatofsolution.pdf
6. Zumdahl, S. A., & Zumdahl, S. S. (2006). Chemistry. In S. A. Zumdahl, & S. S.
Zumdahl, Chemistry (pp. 489 - 492). Urbana: Houghton Mifflin.
7. Haase, R. In Physical Chemistry: An Advanced Treatise; Jost, W., Ed.; Academic:
New York, 1971; p 29.
8. Laidler, K. The World of Physical Chemistry; Oxford University Press: Oxford,
1995; p 110.
9. C.Kittel, H.Kroemer In Thermal Physics; S.R Furphy and Company, New York,
1980; p246
10.DeHoff, R. Thermodynamics in Materials Science: 2 ed.; Taylor and Francis
Group, New York, 2006.

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APPENDIX A: Sample Calculation
a. At various other temperatures, the solubility of benzoic acid was found and values
recorded in the table below:
Solubility (mol solute/L solution) Temperature (k)
0.0421 293
0.0470 304
0.0510 313
0.0554 323

b. Temperature conversion T(K) = 273 + (T) 0C; T(K) = 273 + 50; T(K) = 323K
c. Volume Conversion: 1mL = 0.001L
d. The averages of the volumes can be gotten from the two sets of each using the formula
Average V,
∑f x
V=
n
V 1+V 2
V=
2
e. The Van’t Hoff Equation
Under standard conditions
Under standard conditions, the van 't Hoff equation is
d lnk −∆ H
=
dT RTxT
where ln denotes natural logarithm and R is the ideal gas constant. This equation is
exact at any one temperature. In practice, the equation is often integrated between two
temperatures under the assumption that the reaction enthalpy ΔH is constant. Since in
reality ΔH and the reaction entropy ΔS do vary with temperature for most processes,
the integrated equation is only approximate.
A major use of the integrated equation is to estimate a new equilibrium constant at a
new absolute temperature assuming a constant standard enthalpy change over the
temperature range.

Development of thermodynamics
Combining the definition of Gibbs free energy:
∆𝐺 = ∆𝐻 − 𝑇∆𝑆
where S is the entropy of the system. And from the Gibbs free energy isotherm
equation:
∆𝐺 = −𝑅𝑇𝑙𝑛𝐾𝑒𝑞

23
 Equating both equations, we obtain
−𝑅𝑇𝑙𝑛𝐾𝑒𝑞 = ∆𝐻 − 𝑇∆S
−∆ H ∆ S
lnKeq = +
RT R
Differentiation of this expression with respect to the variable T yields the van 't Hoff
equation.
Provided that ΔH and ΔS are constant, the preceding equation gives lnK as a linear
function of and hence is known as the linear form of the van't Hoff equation. Therefore,
when the range in temperature is small enough that the standard reaction enthalpy and
reaction entropy are essentially constant, a plot of the natural logarithm of the
equilibrium constant versus the reciprocal temperature gives a straight line. The slope of
the line may be multiplied by the gas constant R to obtain the standard enthalpy change
of the reaction, and the intercept may be multiplied by R to obtain the standard entropy
change.

APPENDIX B: Nomenclature
a. Solubility (S) is the property of a solid, liquid or gaseous chemical substance called solute to
dissolve in a solid, liquid or gaseous solvent. Solubility is measured in mol/L, mg/L, mol/kg

b. The equilibrium constant (K) of a chemical reaction is the value of its reaction quotient at
chemical equilibrium, a state approached by a dynamic chemical system after sufficient time
has elapsed at which its composition has no measurable tendency towards further change.

K - Equilibrium constant
x - Solubility
x1 - Solubility at temperature,
T1 x2 - Solubility at temperature, T2
∆𝐻 - Standard enthalpy of solution; kJ/mol
T - Temperature; K
R - Universal gas constant, 8.314Jmol-1k -1
Cb - Concentration of base
Vb - Volume of base
nb - Number of moles of base
nNaOH - Number of moles of NaOH
nbenzoic acid - Number of moles of benzoic acid

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