CHM 101 NOTE Dr.

(Mrs) Falope

ELEMENTARY THERMOCHEMISTRY

Thermochemistry (Chemical thermodynamics) is the study of the heat energy which is

associated with chemical reactions and/or physical transformations. It is a branch
thermodynamics which deals with the relations between heat and other forms of energy (such as
mechanical, electrical, or chemical energy. Chemical thermodynamics is governed by the laws of
thermodynamics. 

A reaction may release or absorb energy, and a phase change may do the same, such as
in melting and boiling. Thermochemistry focuses on these energy changes, particularly on
the system's energy exchange with its surroundings. When a chemical reaction occurs, it is
accompanied by an energy change which may take any of several different forms. For example,
the energy change involved in the combustion of fuels like kerosene, coal, wood, natural gas,
etc., takes the form of heat and light. Electrical energy is obtained from chemical reactions in
batteries. The formation of glucose, C6H12O6 by the process of photosynthesis requires the
absorption of light energy from the sun. Thus, we see that the energy change that accompanies a
chemical reaction can take different forms. In this lesson, you shall study the reactions in which
heat is either evolved or absorbed.

Thermodynamic Systems
In thermodynamics, we must be very precise in our use of certain words. The two most important
of these are system and surroundings. A thermodynamic system is that part of the world
(specific portion of matter) to which we are directing our attention Surrounding
Everything outside the system that has a direct influence on the behaviour of the system is
known as the surroundings. The system and surroundings are separated by a boundary.

If our system is one mole of a gas in a container, then the boundary is simply the inner wall of
the container itself. The boundary need not be a physical barrier; for example, if our system is a
factory or a forest, then the boundary can be wherever we wish to define it. The system boundary
may be real or imaginary, fixed or deformable.
There are three types of systems:
 Isolated System – An isolated system cannot exchange both energy and mass with its
surroundings. The universe is considered an isolated system.
 Closed System – Across the boundary of the closed system, the transfer of energy takes
place but the transfer of mass doesn’t take place. Refrigerator, compression of gas in the
piston-cylinder assembly are examples of closed systems. The tea in a closed Thermos
bottle approximates a closed system over a short time interval.

 Open System – In an open system, the mass and energy both may be transferred between
the system and surroundings. A steam turbine is an example of an open system.

Properties and the State of a System

Any characteristic of a system is called a property. The properties of a system are those
quantities such as the pressure, volume, temperature, and its composition, which are in principle
measurable and capable of assuming definite values. There are of course many properties other
than those mentioned above; the density and thermal conductivity are two examples. However,
the pressure, volume, and temperature have special significance because they determine the
values of all the other properties; they are therefore known as state properties because if their
values are known then the system is in a definite state.

Thermodynamic properties are defined as characteristic features of a system, capable of

specifying the system’s state. Thermodynamic properties may be extensive or intensive.

 Intensive properties are properties that do not depend on the quantity of matter. Pressure
and temperature are intensive properties.
 In the case of extensive properties, their value depends on the mass of the system.
Volume, energy, and enthalpy are extensive properties.

Thermodynamic Process and Cycle

A system undergoes a thermodynamic process when there is some energetic change within the
system that is associated with changes in pressure, volume and internal energy. 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
There are four types of thermodynamic process that have their unique properties, and they are:

 Adiabatic Process – A process where no heat transfers into or out of the system occurs.
 Isochoric/Isometric Process – A process where no change in volume occurs and the
system does no work.
 Isobaric Process – A process in which no change in pressure occurs.
 Isothermal Process – A process in which no change in temperature occurs.
A thermodynamic cycle is a process, or a combination of processes conducted such that the
initial and final states of the system are the same. A thermodynamic cycle is also known as cyclic
operation or cyclic processes.
Thermochemical reactions and equations
All thermochemical reactions are expressed using chemical equations. A thermochemical
equation is the chemical equation for a reaction with the specify heat energy changes and states
of the reactants and products shown in the equation
For writing these equations, we follow the conventions listed below:
(i) The heat evolved or absorbed in a reaction is affected by the physical state of the reacting
substances. Therefore, gaseous, liquid and solid states are represented by putting symbols (g), (l),
and (s) along side the chemical formulae respectively. For example, to represent burning of
methane in oxygen, we write
CH4(g) + 2O2 (g)  CO2 (g) + 2H2O (l) + heat
In writing thermochemical reactions, we denote the amount of heat evolved or absorbed by a
symbol H. The amount of heat evolved or absorbed is written after the equation followed by
semicolon.H is negative for exothermic reactions and it is positive for endothermic reactions.
For example: An exothermic reaction is written as
CH4 (g) + 2O2 (g)  CO2 (g) + 2H2O (l) ; H = – 891 kJ
Whereas an endothermic reaction is written as H2 (g) + I2 (g)  2HI (g) ; H = 52.2 kJ
(ii) In case of elements which exhibit allotropy, the name of allotropic modification is
mentioned. For example, C (graphite), C (diamond), etc.
(iii) The substances in aqueous solutions are specified using the symbol (aq). For example NaCl
(aq) stands for an aqueous solution of sodium chloride
(iv) Thermochemical equations may be balanced even by using fractional coefficients, if so
required. The coefficients of the substances of the chemical equation indicate the number of
moles of each substance involved in the reaction and the H values given correspond to these
quantities of substances.
(v) In case the coefficients are multipied or divided by a factor, H value must also be
multiplied or divided by the same factor. In such cases, the H value will depend upon the
coefficients. For example, in equation.
H2 (g) + 1/2 O2 (g)  H2O (g) ; H = – 242 kJ
If coefficients are multiplied by 2, we would write the equation
2H2 (g) + O2 (g)  2H2O (g) ; H = 2 (– 242) = – 484 kJ
(vi) When the equation is reversed, the sign of H is reversed.
H2 (g) + 1/2 O2 (g)  H2O (l) ; H = – 285.84 kJ
H2O (l)  H2 (g) + 1/2 O2 (g) ; H = + 285.84 kJ
Most of the chemical reactions occur at constant pressure, so the heat of reaction can therefore be
presented by the enthalpy function, H. the enthalpy changes for the reaction is the difference
between the enthalpies of the different states or the reactants and the products.
H = Hprod - Hreact
Calculation
1. Given the stoichiometric equation:
4A + 8C + 12D  8F + 16B ; H = -32.4 Kj
Calculate the H for the following:
a) 12A + 24C + 36D  24F + 48B
b) 2A + 4C + 6D  4F + 8B
c) 2F + 4B  A + 2C + 3D
d) 40F + 80B  20A + 40C + 60D
2. Given that the enthalpy of vaporization for water is: H 2O (l)  H2O(g), Hvap = +44KJ/mol.
Calculate the H for each of the following:
a) evaporating 3moles of H2O (l)
b) evaporating 3g of H2O (l)
c) condensing 3moles of H2O (g)
d) condensing 3moles of H2O (g)
3. given that H2O (l) = -285.83, H2O (g) = -241.82, CO2 (aq) = -413.82, CO2 (g) = -393.5,
CH4(g) = -74.81, CO(g) = -110.53, H2CO3(aq) = -699.69KJ/mol, . Calculate the enthalpy of the
following reactions:
a) H2O (l) + CO2 (aq)  H2CO3 (aq)
b) CH4 (g) + 2O2 (g)  2H2O (g) + CO2(g)
c) 2CH4 (g) + 3O2 (g)  4H2O (g) + 2CO(g)
d) CH4 (g) + O2 (g)  2H2O (g) + C(s)

Laws of Thermodynamics
Thermodynamics laws define the fundamental physical quantities like energy, temperature and
entropy that characterize thermodynamic systems at thermal equilibrium. These thermodynamics
laws represent how these quantities behave under various circumstances.
There are four laws of thermodynamics and are given below:

 Zeroth law of thermodynamics

 First law of thermodynamics
 Second law of thermodynamics
 Third law of thermodynamics
Zeroth Law of Thermodynamics
The Zeroth law of thermodynamics states that if two bodies are individually in equilibrium with
a separate third body, then the first two bodies are also in thermal equilibrium with each other.
This means that if system A is in thermal equilibrium with system C and system B is also in
equilibrium with system C, then system A and B are also in thermal equilibrium.
An example demonstrating the Zeroth Law

Consider two cups A and B with boiling water. When a thermometer is placed in cup A, it gets
warmed up by the water until it reads 100 °C. When it read 100 °C, we say that the thermometer
is in equilibrium with cup A. When we move the thermometer to cup B to read the temperature,
it continues to read 100 °C. The thermometer is also in equilibrium with cup B. By keeping in
mind the zeroth law of thermodynamics; we can conclude that cup A and cup B are in
equilibrium with each other.
The zeroth law of thermodynamics enables us to use thermometers to compare the temperature
of any two objects that we like.

First Law of Thermodynamics

First law of thermodynamics, also known as the law of conservation of energy, states that energy
can neither be created nor destroyed, but it can be changed from one form to another.
First Law Of Thermodynamics Examples:

 Plants convert the radiant energy of sunlight to chemical energy through photosynthesis.
We eat plants and convert the chemical energy into kinetic energy while we swim, walk,
breathe, and scroll through this page.
 Switching on light may seem to produce energy, but it is electrical energy that is
converted.

A way of expressing this law that is generally more useful in Chemistry is Remember this
important equation:
ΔU = q - w

ΔU is the change in internal energy U of the system,

q is the sum of all heat transfer into and out of the system. Takes a +ve sign when heat is
transferred into the system and –ve sign when heat is given out of the system.

w is the net workdone on or by the system. Takes a +ve sign when work is done by the
surrounding on the system and –ve sign when work is done by the system.

Calculations

a) Calculate the heat content when a system does work of 72J and its internal energy is decreased
by 90J.

b) Suppose there is heat transfer of 40J to a system while the system does 10J of work. What is
its internal energy.

c) What is the change in internal energy of a system when a total of 150 J of heat transfer occurs
out of the system and 159J of work is done on the system

What is Enthalpy?
Enthalpy is the measurement of energy in a thermodynamic system. The quantity of enthalpy
equals the total heat content of a system, equivalent to the system’s internal energy plus the
product of volume and pressure.
Mathematically, the enthalpy, H, equals the sum of the internal energy, E, and the product
of the pressure, P, and volume, V, of the system.
H = E + PV

Second Law of Thermodynamics

Second law of thermodynamics states that the entropy in an isolated system always increases.
Any isolated system spontaneously evolves towards thermal equilibrium—the state of maximum
entropy of the system.
The entropy of the universe only increases and never decreases. Many individuals take this
statement lightly and for granted, but it has an extensive impact and consequence.
The second law of thermodynamics can also be stated that "all spontaneous processes produce
an increase in the entropy of the universe". Entropy is the thermodynamic function used to
measure the randomness or disorder.
For example, the entropy of a solid, where the particles are not free to move, is less than the
entropy of a gas, where the particles will fill the container.
Visualizing the second law of thermodynamics
If a room is not tidied or cleaned, it invariably becomes more messy and disorderly with time.
When the room is cleaned, its entropy decreases, but the effort to clean it has resulted in
increased entropy outside the room exceeding the entropy lost.
Mathematically, the second law of thermodynamics is represented as;
ΔSuniv > 0
ΔG=ΔH−TΔS
ΔH
When ΔG = 0, then; ΔS =
T
 ΔH refers to the heat change for a reaction. A positive ΔHΔH means that heat is taken
from the environment (endothermic). A negative ΔHΔH means that heat is emitted or
given the environment (exothermic).
 ΔG is a measure for the change of a system's free energy in which a reaction takes place
at constant pressure (P) and temperature (T).

According to the equation, when the entropy decreases and enthalpy increases the free energy
change, ΔG, is positive and not spontaneous, and it does not matter what the temperature of the
system is. Temperature comes into play when the entropy and enthalpy both increase or both
decrease. The reaction is not spontaneous when both entropy and enthalpy are positive and at
low temperatures, and the reaction is spontaneous when both entropy and enthalpy are positive
and at high temperatures. The reactions are spontaneous when the entropy and enthalpy are
negative at low temperatures, and the reaction is not spontaneous when the entropy and enthalpy
are negative at high temperatures. Because all spontaneous reactions increase entropy, one can
determine if the entropy changes according to the spontaneous nature of the reaction

Calculations
1. Carbon monoxide, a toxic product from the incomplete combustion of fossil fuels, reacts
with water to form CO2 and H2, as shown in the equation CO(g)+H 2O(g)⇌CO2(g)+H2(g),
for which ΔH° = −41.0 kJ/mol and ΔS° = −42.3 J cal/(mol·K) at 25°C and 1 atm.
 a. What is ΔG° for this reaction?
b. What is ΔG if the temperature is increased to 150°C assuming no change in pressure?
2. Methane and water react to form carbon monoxide and hydrogen according to the
equation CH4(g) + H2O(g) ⇌ CO(g) + 3H2(g).
a. What is the standard free energy change for this reaction?
b. State whether the reaction is spontaneous
3. For the reaction: 2H2(g)+O2(g)→2H2O(g)

The enthalpy, ΔH, for this reaction is -241.82 kJ, and the entropy, ΔS, of this reaction is -233.7
J/K. If the temperature is at 25º C, then calculate the standard free energy change, ΔG.

Third Law of Thermodynamics

Third law of thermodynamics states that the entropy of a system approaches a constant value as
the temperature approaches absolute zero.
The entropy of a pure crystalline substance (perfect order) at absolute zero temperature is zero.
This statement holds true if the perfect crystal has only one state with minimum energy.
Third Law Of Thermodynamics Examples:
Let us consider steam as an example to understand the third law of thermodynamics step
by step:

1. The molecules within it move freely and have high entropy.

2. If one decreases the temperature below 100 °C, the steam gets converted to water, where
the movement of molecules is restricted, decreasing the entropy of water.
3. When water is further cooled below 0 °C, it gets converted to solid ice. In this state, the
movement of molecules is further restricted and the entropy of the system reduces more.
4. As the temperature of the ice further reduces, the movement of the molecules in them are
restricted further and the entropy of the substance goes on decreasing.
5. When the ice is cooled to absolute zero, ideally, the entropy should be zero. But in
reality, it is impossible to cool any substance to zero.