Thermochemistry

This topic will cover the following sub-topics:

• Energy
• Heat and Units of Energy
• Specific Heat
• How to calculate specific heat
• Measuring Heat Changes
• Energy and Nutrition
• Energy Values of Food

Energy
Energy is what we use when we perform work or other activities. It can exist in different forms
such as heat, electricity, kinetic (to cause motion), potential (due to position or chemical
composition of a substance) etc. Example of a KE is a car in motion and that of PE includes a
boulder rolling down a hill or a city water tank on top of a platform. We use energy when we walk,
talk, climb, run, think, exercise emotions, eat, think etc. When we are tired, it indicates that we
do not have enough energy in our system to do any work
Sources of energy: varies but includes the food we eat, fossils, fuel etc.
Law of Conservation of Energy. Energy can be converted from one form to another.
Heat and Units of Energy
The SI unit for heat energy is the Joules (J) or Kilojoules (KJ)
Joules (J) is a small amount of energy, so, the KJ is most often used unit for Heat energy. For
example, we need 105J to sleep for one hour which amounts to 100 KJ or we need to use 75000 J
to heat a cup of tea (75KJ)
The Calorie, C, is another unit of heat and is defined as the amount of heat needed to raise 1g of
water by 10C.
1C= 4.184J
Example: 1.0 g of propane fuel was used to cook dinner. 48000 J (48 KJ) of heat was released in
that process. Calculate this amount of heat energy in calories.
Answer: 1 C = 4.184 J, then 48000 J = 48000/4.184 cal = 11, 000 C

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Specific Heat and How to calculate specific heat
Specific Heat
Every substance has the ability to lose or gain heat energy whenever there is a change in
temperature. The amount of heat absorbed or released to reach a certain temperature varies from
one substance to another one. This capacity to absorb or release energy is a physical property and
it is called the
Specific Heat (SH)
SH is defined as the amount of heat (q) needed to raise the temperature of 1.0 g of a
substance by 10C
SH = Heat (q)/mass x ΔT = q/m x ΔT (J(Cal/g0C)
The SH of water = 4.184J/ g0C or 1 cal/ g0C
4.184 J of heat will raise 1g of water by 10C. The same amount of heat will raise 1 g of copper by
100C and 1g of Al by 50C.This indicates that water has a higher capacity than Cu or Al and also it
has a higher capacity to absorb or release heat, therefore, it keeps the body temperature constant
Low amount of SH for Cu and Al relative to water shows that they transfer heat more efficiently
than water hence they are used as cooking wares and are better heat transfer substances.
Calculating Specific Heat (SH)
What is the SH of lead if 530 J is added to raise the temperature of 35.6 g of lead by 12.5 0C?
Answer: SH = q/m ΔT
= 530/35.6 x 12.5 = 0.128 J/g0C
We can calculate amount of heat (q) or the mass of a substance by the following
equation
Q = SH x m ΔT J and m = q/SH x ΔT
Measuring Heat Changes
A calorimeter is used to measure temperature changes when a substance loses or gain heat. A
laboratory scale bomb calorimeter can be made with a Styrofoam cup (reactor) placed in another
(bigger) Styrofoam cup (insulator). One may lag the insulator cup with glass wool
• Place a certain amount of water in the reactor and measure its temperature (Initial temp, T1).
• Heat a certain object to a known temperature and drop it inside the water and immediately cover
the calorimeter.
• Stir the water continuously and measure its temperature at specific intervals. Stir until its
temperature is constant and record it as the final temperature T2. Measure heat change by using

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the formula ΔT = T2 – T1. Heat lost by the object is equal to the heat gained by the water
(qobject=qwater)
Q = SH x m x ΔT.
Energy and Nutrition
The food we eat produces energy for us to do work. Our body grow, sleep, respires etc as a result
of energy supply from the food we eat.
There are different types of food and all of them possesses a measure of energy
Types of food include: Carbohydrate (main source of energy), fats and proteins. (secondary source
of energy if carbohydrate is not available).
Food energy is measured in calories or kilocalories. In nutrition unit, the calorie is written with a
capital Cal. This implies that 1000 Cal = 1 Kcal.
We can also use KJ in nutrition unit. Remember that 1 Cal= 4.184KJ= 4184J. For example, baked
potato = 120 Cal = 4.184 x 120KJ ~ 500 J.
Energy Values of Food
Energy values of food are Kcal or KJ obtained by completely burning of 1g of food

Module 8 Practice Questions

(1) 1.0 g of iron has temperature of 210C. What is the final temperature of the iron sample when
4.184 J is added? (SHiron = 0.492 J/g0C, SHwater= 4.184 J/g0C).
(2) Define (i) the specific heat capacity (ii) calorie.
(3) 1.0 g of propane fuel was used to cook dinner. 48000 J (48 KJ) of heat was released in that
process. Calculate this amount of heat energy in calories
(4) Which instrument can be used to measure specific heat capacity of a substance
(5) If you don’t have a bomb calorimeter in your laboratory, what can you do to measure the
specific heat capacity of a metal object?

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(6) Describe how you will use the equipment described in question 71 to measure specific heat
capacity
(7) How can you determine the specific heat capacity of 1.0 g of yam?

Thermodynamics
The following topics will be covered:
• The first law of thermodynamics
• The second law of thermodynamics
• The third law of thermodynamics
• Zeroth Law of Thermodynamics
Laws of Thermodynamics
There are four laws of thermodynamics which define the fundamental physical quantities such
as temperature, energy and entropy that characterizes thermodynamic systems.
The laws describe how these quantities behave under various circumstances, and prohibit certain
phenomena such as perpetual motion to occur.
First Law of thermodynamics
The first law of thermodynamics provides the basic definition of thermodynamic energy (which is
also called internal energy) associated with all thermodynamic systems. It explains the rule of
conservation of energy in nature.
The law states that energy can be transformed, i.e., changed from one form to another, but cannot
be created or destroyed. Because energy is conserved, the internal energy of a system changes as
heat flows in or out of it. Equivalently, machines that violate the first law (perpetual motion
machines) are impossible. Heat is the flow of thermal energy from one object to another.

For example, wood (stored chemical energy) can be burnt (heat) and used to boil water. The heat
energy from the boiling water can be used to drive a turbine to produce electricity (electrical
energy). The electricity can be used to lighten a bulb (luminous energy) or play a radio (sound
energy) etc
The example shows that energy cannot be created or destroyed, it can only be converted from one
form of energy to another form of energy. The first law can also be formulated by stating that the
change in the internal energy of a system is equal to the amount of heat supplied to the system,
minus the amount of work performed by the system on its surroundings
ΔUsystem = Q-W

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For a thermodynamic cycle of a closed system, which returns to its original state, the heat Qin
supplied to a closed system in one stage of the cycle, minus that Qout removed from it in another
stage of the cycle, equals the net work done by the system.
ΔUsystem (full cycle) = 0 because Q = Qin – Qout = W
The increase in internal energy of a closed adiabatic system can only be the result
of the net work performed by the system, because Q = 0.
ΔUsystem (full circle) = Ufinal – Uinitial = -W

Second Law of Thermodynamics

The concept of energy in the first law does not account for the observation that natural processes
have a preferred direction of progress. For example, spontaneously, heat always flows to regions
of lower temperature, never to regions of higher temperature without external work being
performed on the system.
The first law is deals completely with moving from an initial state to a final state of an evolving
system.
The second law refers to a wide variety of processes, reversible and irreversible. All natural
processes are irreversible. Reversible processes are a convenient theoretical fiction and do not
occur in nature. A prime example of irreversibility is in the transfer of heat by conduction or
radiation.
The second law of thermodynamics asserts the irreversibility of natural processes, and the
tendency of natural processes to lead towards spatial homogeneity of matter and energy, and
especially of temperature. It can be formulated in a variety of interesting and important ways.
The explanation of this phenomenon can be made through the second law of thermodynamics.
A new physical property called the entropy is used by the second law of thermodynamics to
explain this phenomenon.
A change in the entropy (S) of a system is the infinitesimal transfer of heat (Q) to a closed system
driving a reversible process, divided by the equilibrium temperature(T) of the system.
dS= dQ/T
For a closed thermodynamic system, it is a quantitative measure of the amount of thermal energy
not available to do work.
The second law also talks about the kinds of irreversibility other than heat transfer, such as friction,
viscosity, and those of chemical reactions. The notion of entropy is needed to provide a wider
scope of the law
One can also look at entropy from different angles such as:

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• A measure of the disorder or randomness in a closed system.
• A measure of the loss of information in a transmitted message.

• The tendency for all matter and energy in the universe to evolve toward a state of
inert uniformity.
• Inevitable and steady deterioration of a system or society.

The third law of thermodynamics: The entropy of any pure substance in thermodynamic
equilibrium approaches zero as the temperature approaches zero. The entropy of a system at
absolute zero is typically zero, and in all cases is determined only by the number of different
ground states it has.
It is sometimes stated that the entropy of a perfect crystal of any pure substance approaches zero
as the
temperature approaches absolute zero.
At zero temperature the system must be in a state with the minimum thermal energy. This statement
holds true if the perfect crystal has only one state with minimum energy. Entropy is related to the
number of possible microstates according to:
S= kB InΩ
where S is the entropy of the system, kB Boltzmann's constant, and Ω the number of microstates
(e.g. possible configurations of atoms). At absolute zero there is only 1 microstate possible (Ω=1
as all the atoms is identical for a pure substance and as a result all orders are identical as there is
only one combination) and ln (1) = 0.
It may also be stated as: The entropy of a system approaches a constant value as the temperature
approaches zero. The constant value (not necessarily zero) is called the residual entropy of the
system.
Zeroth Law of thermodynamics: If two systems are in thermal equilibrium with a third system,
they must be in thermal equilibrium with each other. This law helps define the notion of
temperature.
Closed and Open Systems
A system is defined as a quantity of matter or a region in space chosen for study. The mass or
region outside the system is called the surroundings.

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Fig. : System, surroundings, and boundary
Boundary: the real or imaginary surface that separates the system from its surroundings. The
boundaries of a system can be fixed or movable. Mathematically, the boundary has zero
thickness, no mass, and no volume.
Closed system or control mass: consists of a fixed amount of mass, and no mass can cross its
boundary. But, energy in the form of heat or work, can cross the boundary, and the volume of a
closed system does not have to be fixed.
Open system or control volume: is a properly selected region in space. It usually encloses a
device that involves mass flow such as a compressor. Both mass and energy can cross the
boundary of a control volume.
Important note: some thermodynamics relations that are applicable to closed and open systems
are different. Thus, it is extremely important to recognize the type of system we have before start
analyzing it.
Isolated system: A closed system that does not communicate with the surroundings by any
means.
Rigid system: A closed system that communicates with the surroundings by heat only.

Adiabatic system: A closed or open system that does not exchange energy with the surroundings
by heat.

Fig. : Closed system, mass cannot cross the boundaries, but energy can
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Fig. Control volume, both mass and energy can cross the boundaries.

Energy
In thermodynamics, we deal with change of the total energy only. Thus, the total energy of a
system can be assigned a value of zero at some reference point. Total energy of a system has two
groups: macroscopic and microscopic.
Macroscopic forms of energy: forms of energy that a system possess as a whole with respect to
some outside reference frame, such as kinetic and potential energy. The macroscopic energy of a
system is related to motion and the influence of some external effects such as gravity, magnetism,
electricity, and surface tension.
Kinetic energy: energy that a system possess as a result of its relative motion relative to some
reference frame, KE

where V is the velocity of the system in (m/s).

Potential energy: is the energy that a system possess as a result of its elevation in a gravitational
field, PE

where g is the gravitational acceleration and z is the elevation of the center of gravity of the system
relative to some arbitrary reference plane.
Microscopic forms of energy: are those related to molecular structure of a system. They are
independent of outside reference frames. The sum of microscopic energy is called the internal
energy, U. The total energy of a system consists of the kinetic, potential, and internal energies:

where the contributions of magnetic, electric, nuclear energy are neglected. Internal energy is
related to the molecular structure and the degree of molecular activity and it may be viewed as the
sum of the kinetic and potential energies of molecules.
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 The sum of translational, vibrational, and rotational energies of molecules is the kinetic
energy of molecules, and it is also called the sensible energy. At higher temperatures, system
will have higher sensible energy.
 Internal energy associated with the phase of a system is called latent heat. The
intermolecular forces are strongest in solids and weakest in gases.
 The internal energy associated with the atomic bonds in a molecule is called chemical or
bond energy. The tremendous amount of energy associated with the bonds within the nucleolus
of atom itself is called atomic energy. Energy interactions with a closed system can occur via
heat transfer and work.
Properties of a System
From the macroscopic perspective, a system is viewed as a continuous, homogeneous matter called
continuum, which consists of a huge number of interacting molecules distributed throughout the
system. The interactions between the molecules are so frequent that the physical or bulk properties
of the system do NOT depend on the behaviour of individual molecules. This hypothesis is valid in
a wide range of engineering applications. It allows the physical properties of a system, such as
pressure, density, and temperature, to be defined as a continuous function at any point of the
system.
The following thermodynamic properties are typically used to describe the interactions between a
system and its surroundings:
 mass m
 pressure P
 temperature T
 volume V and specific volume v
 internal energy U and specific internal energy u
 enthalpy H and specific enthalpy h
 entropy S and specific entropy s
These properties can be classified into two categories based on their dependence on the mass of a
system.

Intensive properties: depend on the mass of a system. Properties, such as mass mm, volume V,
internal energy U, enthalpy H, and entropy S are extensive properties. Their values change
accordingly as the mass of a system changes.
Extensive properties: are independent of the mass of a system. Pressure PP, temperature TT,
specific volume vv, specific internal energy uu, specific enthalpy hh, and specific entropy ss are
intensive properties.

State and Equilibrium

At a given state, all the properties of a system have fixed values. Thus, if the value of even one
property changes, the state will change to different one. In an equilibrium state, there are no
unbalanced potentials (or driving forces) within the system. A system in equilibrium experiences
no changes when it is isolated from its surroundings.
Thermal equilibrium: when the temperature is the same throughout the entire system.
Mechanical equilibrium: when there is no change in pressure at any point of the system.
However, the pressure may vary within the system due to gravitational effects.
Phase equilibrium: in a two phase system, when the mass of each phase reaches an equilibrium
level.
Chemical equilibrium: when the chemical composition of a system does not change with time,
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i.e., no chemical reactions occur
Processes and Cycles
Any change a system undergoes from one equilibrium state to another is called a process, and the
series of states through which a system passes during a process is called a path.

Quasi‐equilibrium process: can be viewed as a sufficiently slow process that allows the system to
adjust itself internally and remains infinitesimally close to an equilibrium state at all times. Quasi‐
equilibrium process is an idealized process and is not a true representation of the actual process.
We model actual processes with quasi‐equilibrium ones. Moreover, they serve as standards to
which actual processes can be compared. Process diagrams are used to visualize processes. Note
that the process path indicates a series of equilibrium states, and we are not able to specify the
states for a non‐quasi‐ equilibrium process.
Prefix iso‐ is used to designate a process for which a particular property is constant.
 Isothermal: is a process during which the temperature remains constant
 Isobaric: is a process during which the pressure remains constant
 Isochoric: is process during which the volume remains constant.
A system is said to have undergone a cycle if it returns to its initial state at the end of the process

Practice Questions
(1) What is the first law of thermodynamics?
(2) Give an example that can demonstrate the first law of thermodynamics?
(3) Explain the second law of thermodynamics with examples?
(4) Describe entropy in four different ways

Chemical Equilibrium
Topics that will be discussed here include:
• Rates of Reaction
• Activation Energy (AE)
• Measurement of Rates of Reaction
• Factors Affecting Rate of Reaction
• Equilibrium Constant
• Using Keq to Predict Direction of Reaction
• Le Chatellier's Principle
• Effect of Change in Concentration
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• Effect of a Catalyst
• Changes in Volume and Pressure
• Changes in Temperature
• Equilibrium Constant in a Saturated Solution
• Adding a Common Ion

Introduction
There are different types of reactions: displacement, substitution, complex reaction etc. Some
reactions are slow (aging of metals), some are very slow (reactions of medications in human body)
and some are fast (acids reactions with carbonates, dissolution of sodium in water)
The question then is:
• Why are reactions fast or slow?
• How fast or slow a reaction will go depends on many factors such as concentration,
temperature, pressure etc
Rates of Reaction
Rates of reaction (ROR) is a measure of how fast a reaction will occur. Reactions happen when
molecules, elements or atoms collide with the proper orientation and sufficient energy.
But not all collisions result into a reaction.
Activation Energy (AE)
When the orientation of reactants is okay, there is still a need for enough energy to break the bonds
between the atoms of each reactant for a reaction to occur.
Activation energy is the minimum amount of energy needed to break the bonds between atoms
of reactants. AE is like going from one side of a hill to the other side. We need enough energy to
get to the top of a hill and then can easily run down the hill to the other side.

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Hence conditions for a reaction to occur includes: collision, proper orientation,
concentration and sufficient energy.
Measurement of Rates of Reaction
We can we measure the rates of a reaction by measuring the amount of reactants consumed or
amount of product formed over a given amount of time
R = [Δ in concentration]/Δ in time
For example, we can buy a loaf of bread cut into 20 slices. We can measure how long it will take
us to eat the whole 20 slices of bread. The we can calculate how long it took us to eat each slice of
bread, which indicates the rate of reaction.
Factors Affecting Rate of Reaction
Temperature- increase in temperature increases the rate of a reaction by increasing the rate of
collision, kinetic energy and energy. For example, increasing the heat when we are cooking
increases the rate of cooking also if body temperature increases, the pulse rate and breathing will
also increase. If we decrease temperature, ROR will also decrease. For example, freezing food
decreases the rate of spoilage
Concentration of Reactants- Increase in the concentration of reactants increases the rate of
collision, hence the rate of reaction. Increase in pressure and volume also increases the rate of a
reaction. The converse is also true.
Catalyst: increases or slows down the rate of a reaction by lowering AE or providing and
alternative pathway with a lower AE. So, if AE is lowered, more collision will occur, hence
sufficient energy will be provided to make the reaction occur. For example, Platinum and
Palladium are catalytic converters that convert pollutants form combustion of petrol in an
automobile engine into harmless products. Pollutants in combustion engine include: CO, C8H18
and NO.

Equilibrium Constant
Reaction of reactants goes in forward and backward reaction at the same time and rate. At a certain
time, the rate of the forward reaction and backward reaction will be the same. Then, the reaction
is said to have reached equilibrium. Hence the [Reactants] and [Product] are constant

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Some reactions are heterogeneous, i.e., the reactants and products are in more than one states in a
reaction. The Keq such reaction is called heterogeneous Keq. The concentration of solids and
liquids reactant or product are not included in the equation for equilibrium constant. For example,
in the reaction shown below,

If we know the concentrations of the reactants and the products, we can calculate the Keq for any
reaction
For example, in the reaction of H2g + I2g ↔ 2HIg with the following concentrations: 0.1M 0.2M
1.0M
Keq = [HI]2 /[H2][I2] = [1.0]2/[0.1][0.2] = 0.4
Using Keq to Predict Direction of Reaction
If Ag ↔ Bg, Keq = [B]/[A]
If Keq is large, then [B] >>>> [A], the more product will be formed by the time equilibrium is
reached. Hence the direction of reaction is towards the right.
The converse is also true
Le Chatellier's Principle
• Changes in conditions of reactions such as P, C, T, when a reaction is already in equilibrium,
changes the position of equilibrium.
• Le Chatellier's says that when a stress (change) is placed on a system already at equilibrium, the
equilibrium will change (shift) in the direction that relieves the stress.
• If a system is in equilibrium and a factor of equilibrium such as concentration is changed while
others remain constant, Keq will not change but the concentration of the other components and the
direction of equilibrium will change so as to keep Keq constant.
Effect of Change in Concentration: For example: PCl5g ↔ PCl3g + Cl2g Keq =
[PCl3][Cl2]/[PCl5]= 0.42
If [PCl5] is changed by adding mor PCl5, while P, T are constant, the concentrations of PCl3 and
Cl2 will change, but Keq will not change but moves in the direction of the product.
If [PCl3] and [Cl2] are increased, equilibrium will not change but shift towards the PCl5 while its
value remains constant
Effect of a Catalyst: Addition of a catalyst to a reaction either fastens or slows down the rate of a
reaction
Changes in Volume and Pressure: Volume and pressure are inversely related to each other. But
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changes in their value will only change the direction of equilibrium and not its value
Changes in Temperature: When Temperature is increased, the KE increase in the forward
direction
If the reaction is endothermic and the temperature is increased, the Keq will increase and more
products will be formed, hence the direction of equilibrium will be towards the right. If the
temperature is lowered, equilibrium will shift to the left and the reaction will become exothermic.
Equilibrium Constant in a Saturated Solution
In a saturated solution, some undissolved reactants are in contact with the maximum
number of dissolved solutes. At equilibrium, the rate of dissolution will be equal to the rate of
crystallization at a fixed temperature
CaC2O4s ↔ Ca2+aq + C2O42-aq
Solubility constant of CaC2O4s, Ksp = [Ca2+aq][C 2-
2 4O aq]

Solubility of a solid is constant and is not included in the Ksp

For example: MgCO3s ↔ Mg2+aq + CO32-aq Ksp = [Mg2+][CO32-]

The mole ration of Mg2+/CO32- = 1:1 meaning that their concentration is the same, hence
Ksp = [s][s] = S2 and S = √Ksp

If Ksp= 1.6 x 10-8, then S = √1.6 x 10-8 = 1.3 x 10-4M

Adding a Common Ion

For a sparingly soluble salt like MgCl2s ↔ Mg2+ aq + 2Claq.
Adding Mg2+ which is soluble will increase the amount of Mg2+ ion solution, Ksp will shift
direction to keep its value constant by making more Mg2+ reacting with more Cl- to form MgCl2
hence equilibrium will shift to the left.
This implies that the solubility of a sparingly soluble salt will decrease if a common ion is added.

Practice Questions
1. Define (i) Rates of a reaction (ii) activation energy
2. How does equilibrium constant responds to the change in concentration of Chlorine
in the reaction shown below: PCl5g ↔ PCl3g + Cl2g

3. If the equilibrium constant of a reaction is written as shown below, write the equation for the
reaction: Keq = [HI]2 /[H2][I2]

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4. Write the equilibrium equation for the reactions shown below
CaCO3s → CaOs + CO2g
CO2g + 2H2g →CH3OHl
5. State Le Chatellier's principle?

6. A loaf of bread consists of 20 slices. It took Nwachukwu 15 minutes to eat the 20

slices. What is the rate at which Nwachukwu ate the bread?
7. State 4 parameters that affects the rate of a reaction. Briefly describe how each one
of them affects the rate of a reaction
6. If a reaction is expressed as shown below, write an equation for its equilibrium
constant

• If aA + bB ↔ cC + dD

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