First Law of Thermodynamics

Md. Didarul Islam

 Thermodynamics and Thermochemistry

• Thermodynamics • Thermochemistry

• The study of the flow of heat or any • That part of thermodynamics that deals
other form of energy into or out of a with the relationships between chemical
system as it undergoes a physical or reactions and energy changes involving
chemical transformation, is called heat
Thermodynamic
 Thermodynamics

Scope of Thermodynamics
(1) Most of the important laws of Physical Chemistry, including the van’t Hoff
law of lowering of vapor pressure, Phase Rule and the Distribution Law, can
be derived from the laws of thermodynamics.
(2) It tells whether a particular physical or chemical change can occur under a
given set of conditions of temperature, pressure and concentration.
(3) It also helps in predicting how far a physical or chemical change can
proceed, until the equilibrium conditions are established.
 Thermodynamics

Limitations of Thermodynamics
(1) Thermodynamics is applicable to macroscopic systems consisting of
matter in bulk and not to microscopic systems of individual atoms or
molecules. It ignores the internal structure of atoms and molecules.
(2) Thermodynamics does not bother about the time factor. That is, it does not
tell anything regarding the rate of a physical change or a chemical reaction.
It is concerned only with the initial and the final states of the system.
 Thermodynamics
SYSTEM, BOUNDARY, SURROUNDINGS
A system is that part of the universe which is under thermodynamic study and the rest of
the universe is surroundings.
The real or imaginary surface separating the system from the surroundings is called the
boundary.
 Thermodynamics
HOMOGENEOUS AND HETEROGENEOUS SYSTEMS
When a system is uniform throughout, it is called a Homogeneous System.
Examples are: a pure single solid, liquid or gas, mixtures of gases, and true solution of a
solid in a liquid. A homogeneous system is made of one phase only. A phase is defined as a
homogeneous, physically distinct and mechanically separable portion of a system.
A heterogeneous system is one which consists of two or more phases. In other
words it is not uniform throughout. Examples of heterogeneous systems are: ice in contact
with water, ice in contact with vapor etc. Here ice, water and vapor constitute separate
phases.
 Thermodynamics
TYPES OF THERMODYNAMIC SYSTEMS
There are three types of thermodynamic systems depending on the nature of the boundary. If the boundary is closed or
sealed, no matter can pass through it. If the boundary is insulated, no energy (say heat) can pass through it.
(1) Isolated System
An isolated system is one that can transfer neither matter nor energy to and from its surroundings.
(2) Closed System
A closed system is one which cannot transfer matter but can transfer energy in the form of heat, work and radiation to
and from its surroundings.
(3) Open System
An open system is one which can transfer both energy and matter to and from its surroundings.
 Thermodynamics
STATE OF A SYSTEM
A thermodynamic system is said to be in a certain state when all its properties are fixed.
EQUILIBRIUM AND NON–EQUILIBRIUM STATES
A system in which the state variables have constant values throughout the system is said to be in a
state of thermodynamic equilibrium.
A system in which the state variables have different values in different parts of the system is said
to be in a non-equilibrium state.
 Thermodynamics

The Criteria for Equilibrium

(1) The temperature of the system must be uniform and must be the same as the temperature
of the surroundings (thermal equilibrium).
(2) The mechanical properties must be uniform throughout the system (mechanical
equilibrium). That is, no mechanical work is done by one part of the system on any other
part of the system.
(3) The chemical composition of the system must be uniform with no net chemical change
(chemical equilibrium).
If the system is heterogeneous, the state variables of each phase remain constant in each phase.
 Thermodynamics
THERMODYNAMIC PROCESSES
When a thermodynamic system changes from one state to another, the operation is called a Process. These
processes involve the change of conditions (temperature, pressure and volume). The various types of
thermodynamic processes are:
(1) Isothermal Processes
Those processes in which the temperature remains fixed, are termed isothermal processes.
For an isothermal process dT = 0
(2) Adiabatic Processes
Those processes in which no heat can flow into or out of the system, are called adiabatic processes. For an
adiabatic process dq = 0
(3) Isobaric Processes
Those processes which take place at constant pressure are called isobaric processes.
For an isobaric process dp = 0
(4) Isochoric Processes
Those processes in which the volume remains constant are known as isochoric processes.
For isochoric processes dV = 0
(5) Cyclic Process
When a system in a given state goes through a number of different processes and finally returns to its initial state,
the overall process is called a cycle or cyclic process.
For a cyclic process dE = 0, dH = 0.
Thermodynamics
 Thermodynamics
REVERSIBLE AND IRREVERSIBLE PROCESSES
 Thermodynamics
NATURE OF HEAT AND WORK
When a change in the state of a system occurs, energy is transferred to or from the
surroundings. This energy may be transferred as heat or mechanical work.
We shall refer the term ‘work’ for mechanical work which is defined as force × distance.
Units of Work
In CGS system the unit of work is erg
Since the erg is so small, a bigger unit, the joule (J) is now used.
1 joule = 107 ergs
Units of Heat
The unit of heat, which was used for many years, is calorie (cal). A calorie is defined as
the quantity of heat required to raise the temperature of 1 gram of water by 1°C in the
vicinity of 15°C.
Since heat and work are interrelated, SI unit of heat is the joule (J).
1 cal = 4.184 J
 Thermodynamics
Sign Convention of Heat
The symbol of heat is q. If the heat flows from the surroundings into the system to raise the
energy of the system, it is taken to be positive, +q. If heat flows from the system into the
surroundings, lowering the energy of the system, it is taken to be negative, –q.
Sign Convention of Work
The symbol of work is w. If work is done on a system by the surroundings and the energy of
the system is thus increased, it is taken to be positive, +w. If work is done by the system on the
surroundings and energy of the system is decreased, it is taken to be negative, –w.
 Thermodynamics
FIRST LAW OF THERMODYNAMICS
The first law of thermodynamics is, in fact, an application of the broad principle known as the Law
of Conservation of Energy to the thermodynamic system.
It states that: the total energy or internal energy of an isolated system remains constant
though it may change from one form to another.
When a system is changed from state A to state B, it undergoes a change in the internal energy
from 𝐸𝐴 to 𝐸𝐵 . Thus, we can write
∆𝐸 = 𝐸𝐵 − 𝐸𝐴
This energy change is brought about by the evolution or
absorption of heat and/or by work being done by the system.
Because the total energy of the system must remain constant,
we can write the mathematical statement of the First Law as:
∆𝐸 = 𝑞 − 𝑤
Where,
q = the amount of heat supplied to the system
w = work done by the system
Thus First Law may also be stated as: the net energy change
of a closed system is equal to the heat transferred to the
system minus the work done by the system.
 Thermodynamics
Some Special Forms of First Law of Thermodynamics
Mathematical statement of the First law of Thermodynamics is
∆𝐸 = 𝑞 − 𝑤
Case 1: For a cyclic process involving isothermal expansion of an ideal gas
∆𝐸 = 0
𝑞=𝑤
Case 2: For an isochoric process (no change in volume) there is no work of expansion i.e. w = 0.
Hence ∆𝐸 = 𝑞𝑣
Case 3: For an adiabatic process there is no change in heat gained or lost i.e. q = 0. Hence
∆𝐸 = −𝑤
In other words, the decrease in internal energy is exactly equal to the work done on the system by
surroundings.
Case 4: For an isobaric process there is no change in pressure, i.e. P remains constant. Hence
∆𝐸 = 𝑞 − 𝑤
∆𝐸 = 𝑞 − 𝑃∆𝑉
Thermodynamics
Thermodynamics
 Thermodynamics
ENTHALPY OF A SYSTEM
In a process carried at constant volume (say in a sealed tube), the heat content of a system is the same as
internal energy (E), as no PV work is done. But in a constant-pressure process, the system (a gas) also
expends energy in doing PV work.
Therefore, the total heat content of a system at constant pressure is equivalent to the internal energy
E plus the PV energy. This is called the Enthalpy of the system and is represented by the symbol H. Thus
enthalpy is defined by the equation:
𝐻 = 𝐸 + 𝑃𝑉
Change in Enthalpy
If ΔH be the difference of enthalpy of a system in the final state (𝐻2 ) and that in the initial state (𝐻1 ),
∆𝐻 = 𝐻2 − 𝐻1
Substituting the values of 𝐻2 and 𝐻1
∆𝐻 = 𝐸2 + 𝑃2 𝑉2 − 𝐸1 + 𝑃1 𝑉1
∆𝐻 = 𝐸2 − 𝐸1 + 𝑃2 𝑉2 − 𝑃1 𝑉1
∆𝐻 = ∆𝐸 + ∆𝑃𝑉
 Thermodynamics
If P is constant while the gas is expanding, we can write
∆𝐻 = ∆𝐸 + 𝑃∆𝑉
∆𝐻 = ∆𝐸 + 𝑤 … … … … … … . . (1)
According to the First Law,
∆𝐸 = 𝑞 − 𝑤 … … … … … … . . (2)
From equations (1) and (2)
∆𝐻 = 𝑞 when change in state occurs at constant pressure
This relationship is usually written as
∆𝐻 = 𝑞𝑝
where subscript p means constant pressure.
Thus ΔH can be measured by measuring the heat of a process occurring at constant pressure.
 Thermodynamics
MOLAR HEAT CAPACITIES
By heat capacity of a system we mean the capacity to absorb heat and store energy. As the system
absorbs heat, it goes into the kinetic motion of the atoms and molecules contained in the system.
This increased kinetic energy raises the temperature of the system.
If q calories is the heat absorbed by mass m and the temperature rises from 𝑇1 to 𝑇2 ,
the heat capacity (c) is given by the expression
𝑞
𝑐= … … … … … … (1)
𝑚 𝑇2 − 𝑇1

Thus heat capacity of a system is the heat absorbed by unit mass in raising the temperature by
one degree (K or ºC) at a specified temperature.
When mass considered is 1 mole, the expression (1) can be written as
𝑞 𝑞
𝐶= =
𝑇2 − 𝑇1 ∆𝑇
where C is denoted as Molar heat capacity.
 Thermodynamics

The molar heat capacity of a system is defined as the amount of heat required to raise the
temperature of one mole of the substance (system) by 1 K.
Since the heat capacity (C) varies with temperature; its true value will be given as
𝑑𝑞
𝐶=
𝑑𝑇
where dq is a small quantity of heat absorbed by the system, producing a small temperature rise dT.
Thus, the molar heat capacity may be defined as the ratio of the amount of heat absorbed to the
rise in temperature.
 Thermodynamics
Molar Heat Capacity at Constant Volume
According to the first law of thermodynamics
𝑑𝐸 = 𝑑𝑞 − 𝑃𝑑𝑉
𝑑𝑞 = 𝑑𝐸 + 𝑃𝑑𝑉
From molar heat capacity equation
𝑑𝑞 𝑑𝐸 + 𝑃𝑑𝑉
𝐶= =
𝑑𝑇 𝑑𝑇
At constant volume dV = 0, the equation reduces to
𝑑𝑞
𝐶=
𝑑𝑇
𝑑𝐸
𝐶𝑉 =
𝑑𝑇 𝑉

Thus the heat capacity at constant volume is defined as the rate of change of internal energy
with temperature at constant volume.
 Thermodynamics
Molar Heat Capacity at Constant Pressure
From molar heat capacity definition 𝑑𝑞
𝐶=
𝑑𝑇
𝑑𝐸 + 𝑃𝑑𝑉
𝐶=
𝑑𝑇
𝑑𝐸 𝑑𝑉
𝐶= +𝑃 … … … … (1)
𝑑𝑇 𝑑𝑇
From the defination of heat of enthalpy
𝐻 = 𝐸 + 𝑃𝑉
Differentiating this equation w.r.t T at constant pressure, we get
𝑑𝐻 𝑑𝐸 𝑑𝑉
= +𝑃 … … … … (2)
𝑑𝑇 𝑃
𝑑𝑇 𝑃
𝑑𝑇 𝑃
comparing it with equation (1) and (2) we have
𝑑𝐻
𝐶𝑃 =
𝑑𝑇 𝑃

Thus heat capacity at constant pressure is defined as the rate of change of enthalpy with
temperature at constant pressure.
 Thermodynamics
Relation Between 𝑪𝑷 and 𝑪𝑽
From the definitions, it is clear that two heat capacities are not equal and 𝐶𝑃 is greater than 𝐶𝑉 by a factor which
is related to the work done. At a constant pressure part of heat absorbed by the system is used up in increasing the
internal energy of the system and the other for doing work by the system. While at constant volume the whole of
heat absorbed is utilized in increasing the temperature of the system as there is no work done by the system. Thus
increase in temperature of the system would be lesser at constant pressure than at constant volume. Thus 𝐶𝑃 is
greater than 𝐶𝑉
𝑑𝐻 𝑑𝐸
𝐶𝑃 = 𝐶𝑉 =
𝑑𝑇 𝑑𝑇
By definition H = E + PV for 1 mole of an ideal gas
𝐻 = 𝐸 + 𝑅𝑇
Differentiating this equation w.r.t T, we get
𝑑𝐻 𝑑𝐸
= +𝑅
𝑑𝑇 𝑑𝑇
𝐶𝑃 = 𝐶𝑉 + 𝑅
𝐶𝑃 − 𝐶𝑉 = 𝑅
Thus 𝐶𝑃 is greater than 𝐶𝑉 by a gas constant whose value is 1.987 calK–1mol–1 or 8.314 JK–1mol–1 in S.I. units.
Thermodynamics
 Thermodynamics
JOULE-THOMSON EFFECT
Joule and Thomson (later Lord Kelvin) showed that when a compressed gas is forced through a
porous plug into a region of low pressure, there is appreciable cooling.
The phenomenon of producing lowering of temperature when a gas is made to expand
adiabatically from a region of high pressure into a region of low pressure, is known as Joule-
Thomson Effect or Joule-Kelvin Effect.
Applications of first law of thermodynamics:
This fundamental principle has numerous applications across various fields. Here are some key applications of the first law of thermodynamics:
1. Heat Engines: The first law of thermodynamics is fundamental to the operation of heat engines, including internal combustion
engines, steam engines, and gas turbines. It governs the conversion of heat energy into mechanical work and vice versa, dictating the
efficiency of these systems.
2. Refrigeration and Air Conditioning: The first law of thermodynamics is applied in refrigeration and air conditioning systems to
transfer heat energy from a low-temperature environment (e.g., inside a refrigerator) to a high-temperature environment (e.g., outside
the refrigerator). This principle enables the cooling of spaces and preservation of perishable goods.
3. Chemical Reactions: In chemical reactions, the first law of thermodynamics governs the conservation of energy, including heat
transfer and work done. It is used to analyze and predict the energy changes associated with chemical processes, such as exothermic
and endothermic reactions.
4. Thermal Power Plants: The first law of thermodynamics is crucial in the design and operation of thermal power plants, including
coal-fired, gas-fired, and nuclear power plants. It governs the conversion of heat energy into electrical energy through processes like
steam generation, turbine operation, and electricity generation.
5. Energy Storage and Conversion: The first law of thermodynamics is applied in energy storage and conversion systems, such as
batteries, fuel cells, and capacitors. It dictates the conservation of energy during charging and discharging processes, as well as the
efficiency of energy conversion between different forms (e.g., chemical energy to electrical energy).
6. Renewable Energy Systems: Renewable energy systems, such as solar photovoltaic panels and wind turbines, rely on the principles of
the first law of thermodynamics to convert natural energy sources (e.g., sunlight, wind) into usable electrical energy. It governs the
efficiency and performance of these energy conversion processes.
7. Heat Exchangers: Heat exchangers utilize the first law of thermodynamics to transfer heat energy between fluid streams at different
temperatures. They are widely used in HVAC systems, industrial processes, and thermal management applications to control
temperatures and improve energy efficiency.
8. Material Processing: The first law of thermodynamics is applied in material processing industries, such as metallurgy and polymer
processing, to optimize energy consumption, control temperatures, and ensure product quality during manufacturing processes like
casting, forging, and extrusion.
 Thermochemistry
Thermochemistry is the branch of physical chemistry which deals with the thermal or heat changes caused by
chemical reactions.
When the internal energy of reactants (𝐸𝑟 ) is greater than the internal energy of the products (𝐸𝑝 ), the difference of
internal energy, ΔE, is released as heat energy. Such a reaction is called exothermic reaction.
∆𝐸 = 𝐸𝑝 − 𝐸𝑟
If the internal energy of the products (𝐸𝑝 ) is greater than that of the reactants (𝐸𝑟 ), heat is absorbed from the
surroundings. Such a reaction is called endothermic reaction. The amount of heat released or absorbed in a chemical
reaction is termed the heat of reaction.
ENTHALPY OF A REACTION
Thermochemical measurements are made either at (a) constant volume or (b) constant pressure. The magnitudes of
changes observed under the two conditions are different.
The change in internal energy (∆E) is the heat change accompanying a chemical reaction at constant volume
because no external work is performed.
The enthalpy of a system is defined as the sum of the internal energy and the product of its pressure and volume.
That is 𝐻 = 𝐸 + 𝑃𝑉
where E is the internal energy, P is the pressure and V is the volume of the system. It is also called Heat content.
∆𝐻 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
∆𝐻 = 𝐻𝑃 − 𝐻𝑅
 Thermochemistry
EXOTHERMIC AND ENDOTHERMIC REACTIONS
Let us consider a general reaction at constant pressure,
A+B→C+D
If 𝐻𝐴 , 𝐻𝐵 , 𝐻𝐶 and 𝐻𝐷 be the enthalpies of A, B, C and D respectively, the heat of reaction at constant
pressure viz., ∆H is equal to the difference in enthalpies of the products and the reactants
𝐻𝐴 = 𝐻𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 − 𝐻𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠
∆𝐻 = 𝐻𝐶 + 𝐻𝐷 − 𝐻𝐴 + 𝐻𝐵

The value of ∆H may be either zero, negative or

positive. Where ∆H is zero, the enthalpies of the
products and reactants being the same, the heat is
evolved or absorbed. In case ∆H is negative, the sum
of enthalpies of the products is less than that of the
reactants and the difference in enthalpy is given out
in the form of heat
 Heat of Reaction
The Heat of Reaction or Enthalpy of Reaction
The heat of reaction (enthalpy of reaction) is the amount of heat energy released or absorbed during a
chemical reaction. The heat of reaction is measured in kilojoules per mole (kJ/mol) of reactants.
The heat of reaction can be used to calculate the amount of heat energy that is released or absorbed in a
chemical reaction.
1. The Heat of Combustion or Enthalpy of combustion
The heat of combustion (enthalpy of combustion) is the heat released during the combustion of a fuel. The
enthalpy of combustion can be determined experimentally by burning a fuel in a bomb calorimeter and
measuring the increase in the temperature of the calorimeter. The enthalpy of combustion is the sum of the
heat of formation of the products of combustion and the heat of vaporization of the water produced.
2. The Heat of Formation or Enthalpy of Formation
This is the heat that is released or absorbed when one mole of a substance is formed from its component
elements in their standard states.
 Heat of Reaction
3. The Heat of Neutralization or Enthalpy of Neutralization
The heat of neutralization, also known as the enthalpy of neutralization, is the amount of heat energy released or
absorbed when an acid and a base react to form water and salt. The heat of neutralization is always exothermic,
meaning it releases energy in the form of heat.
4. The Heat of Solution or Enthalpy of the Solution
The heat of solution (enthalpy of the solution) is the heat released or absorbed when a mole of a solute is dissolved in
a mole of solvent. The heat of solution is a measure of the strength of the interaction between the solute and the
solvent.
The enthalpy of the solution can be positive or negative. A positive enthalpy of the solution means that the
interaction between the solute and the solvent is strong enough to release heat. A negative enthalpy of the solution
means that the interaction between the solute and the solvent is strong enough to absorb heat.
5. The Heat of Hydration or Enthalpy of Hydration
The heat of hydration is the amount of heat energy released when a certain amount of water is added to a chemical
compound. The enthalpy of hydration is the heat of hydration per mole of water added.
 Heat of Reaction
6. The heat of Transition or Enthalpy of Transition

The heat of Transition or Enthalpy of Transition is the amount of heat required to change one mole of a solid into a
liquid at its melting point, or the amount of heat released when one mole of a liquid is converted into a solid at its
freezing point.

7. The Heat of Fusion or Enthalpy of Fusion

The heat of fusion is the heat energy required to change one mole of a substance from a solid to a liquid at its melting
point. The symbol for the heat of fusion is ΔHfus.

The enthalpy of fusion is the same as the heat of fusion.

8. The Heat of Vaporization or Enthalpy of Vaporization

The heat of vaporization is the energy needed to convert a given quantity of liquid into vapor. The enthalpy of
vaporization is the energy needed to convert a given quantity of liquid into vapor, and to vaporize the same amount of
liquid completely.
 Heat of Reaction
9. The Heat of Sublimation or Enthalpy of Sublimation
The heat of sublimation is the amount of heat energy required to convert a solid to a gas. The enthalpy of sublimation is
the amount of heat energy required to convert a solid to a gas at constant pressure.
10. Lattice Energy
The lattice energy is the energy required to break the ionic bonds in a crystal and separate the ions into individual
atoms. The lattice energy is a measure of the strength of the ionic bonds in a crystal.
11. Bond Dissociation Energy or Enthalpy of Bond Dissociation
The energy or enthalpy of bond dissociation is the energy or enthalpy required to break a molecule or ion into its
component atoms.
12. Bond Energy
Bond energy is the energy released when two atoms form a covalent bond. The bond energy is determined by the type
of atoms involved, the distance between them, and the type of bond. The bond energy is typically measured in
kilojoules per mole (kJ/mol).
 Heat of Reaction

The Heat of Reaction (also known and Enthalpy of Reaction)

is the change in the enthalpy of a chemical reaction that occurs at a constant pressure. It is a
thermodynamic unit of measurement useful for calculating the amount of energy per mole either
released or produced in a reaction. Since enthalpy is derived from pressure, volume, and internal energy,
all of which are state functions, enthalpy is also a state function. Given a constant pressure, the change
in enthalpy can be measured as
ΔH = q
How to Calculate ΔH
Experimentally Enthalpy can be measured experimentally through the use of a calorimeter. A
calorimeter is an isolated system which has a constant pressure, so
ΔH = q = Cp × m × ΔT
 Heat of Reaction
How to calculate ΔH Numerically
To calculate the standard enthalpy of reaction the standard enthalpy of formation must be utilized.
Another, more detailed, form of the standard enthalpy of reaction includes the use of the standard
enthalpy of formation ΔH:

∆𝐻 0 = ෍ ∆𝑣𝑝 ∆𝐻0𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ෍ ∆𝑣𝑟 ∆𝐻0𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

Where,
𝑣𝑝 = Stoichiometric coefficient of the product from the balanced reaction
𝑣𝑟 = Stoichiometric coefficient of the reactants from the balanced reaction
∆𝐻 0𝑓 = Standard enthalpy of formation for the reactants or the products

 A positive ΔH° value represents an addition of energy from the reaction (and from the
surroundings), resulting in an endothermic reaction.
 A negative value for ΔH° represents a removal of energy from the reaction (and into the
surroundings) and so the reaction is exothermic.
 Heat of Reaction
Example 1: Calculate the enthalpy change for the combustion of acetylene (C2H2). If the standard values
of∆𝐻0𝑓 are as follows: CO2: - 393.5 KJ/mole, H2O: - 241.8 KJ/mole, and C2H2: + 227 KJ/mole.
Solution
1) The first step is to make sure that the equation is balanced and correct. Remember, the combustion of a
hydrocarbon requires oxygen and results in the production of carbon dioxide and water.

2) Next, locate a table of Standard Enthalpies of Formation to look up the values for the components of the
reaction
3) First find the enthalpies of the products:
∆𝐻0𝑓(CO2 = −393.5 kJ/mole
)

Multiply this value by the stoichiometric coefficient, which in this case is equal to 4 mole
393.5kJ
𝑣𝑝 ∆𝐻0𝑓 CO2 = 4 𝑚𝑜𝑙𝑒 × −
mole
𝑣𝑝 ∆𝐻0𝑓 CO2 = −1574 𝐾𝐽
 Heat of Reaction
∆𝐻0 𝑓(H2O) = −241.8 k JΤm ole

The stoichiometric coefficient of this compound is equal to 2 moles. So,

241.8 kJ
𝑣𝑝 ∆𝐻0𝑓(H2O = 2 𝑚𝑜𝑙𝑒 × − = −483.6 𝐾𝐽
) mole
Now add these two values in order to get the sum of the products

𝑆𝑢𝑚 𝑜𝑓 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠 = ෍ 𝑣𝑝 ∆𝐻0𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) = −1574 𝐾𝐽 − 483.6 𝐾𝐽 = −2057.6 𝐾𝐽

4) Now, find the enthalpies of the reactants:

∆𝐻0𝑓(C2H2 = +227 kJ/mole
)

Multiply this value by the stoichiometric coefficient, which in this case is equal to 2 moles.
227 kJ
𝑣𝑝 ∆𝐻0𝑓(C2H2 = 2 𝑚𝑜𝑙𝑒 × + = +454 𝐾𝐽
) mole
∆𝐻0𝑓(O2 = 0 𝐾𝐽/𝑚𝑜𝑙𝑒
)
 Heat of Reaction
The stoichiometric coefficient of this compound is equal to 5 moles. So,
0 kJ
𝑣𝑝 ∆𝐻0𝑓(O2 = 5 𝑚𝑜𝑙𝑒 × = 0 𝐾𝐽
) mole
Add these two values in order to get the sum of the reactants

𝑆𝑢𝑚 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠 = ෍ 𝑣𝑝 ∆𝐻0𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠) = +454 𝐾𝐽 + 0 𝐾𝐽 = +454 𝐾𝐽

5) The sum of the reactants and products can now be inserted into the formula:

∆𝐻0 = ෍ 𝑣𝑝 ∆𝐻0𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ෍ 𝑣𝑟 ∆𝐻0𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆𝐻0 = −2057.6 𝐾𝐽 − 454 𝐾𝐽

∆𝐻0 = −2511.6 𝐾𝐽
 Heat of Reaction
Example 2: Calculate the enthalpy change for the following reaction.
H2O + CO2 H2CO3
If the standard values of∆𝐻0𝑓 are as follows: CO2: - 393.5 KJ/mole, H2O: - 241.8 KJ/mole, and H2CO3: - 275.2 KJ/mole.
Solution:
∆𝐻0 = ෍ 𝑣𝑝 ∆𝐻0𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ෍ 𝑣𝑟 ∆𝐻0𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆𝐻0 = −275.2 𝐾𝐽 − ( −241.8 𝐾𝐽 + 393.5 𝐾𝐽 )

∆𝐻0 = +360. 1 𝐾𝐽

Example 3: Calculate ΔH if a piece of metal with a specific heat of 0.98 kJ kg−1 K−1 and a mass of 2 kg is
heated from 22 °C to 28 °C
Solution:
∆𝐻 = 𝐶𝑝 × 𝑚 × ∆𝑇
∆𝐻 = 0.98 × 2 × 6
∆𝐻 = 11.76 𝐾𝐽
 Heat of Reaction
Example 4: Large quantities of ammonia are used to prepare nitric acid. The first step consists of the
catalytic oxidation of ammonia to nitric oxide, NO. What is the standard enthalpy change for this reaction?

NH3(g) + 5O2 (g) NO(g) + 6H2O(g)

If the standard values of∆𝐻0𝑓 are as follows: NO: 90.3 KJ/mole, H2O: - 241.8 KJ/mole, and NH3: - 45.9 KJ/mole

Solution:

∆𝐻0 = ෍ 𝑣𝑝 ∆𝐻0𝑓(𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠) − ෍ 𝑣𝑟 ∆𝐻0𝑓(𝑟𝑒𝑎𝑐𝑡𝑎𝑛𝑡𝑠)

∆𝐻0 = (4 +90.3 𝐾𝐽 + 6 −241.8 𝐾𝐽 ) − (4 −45.9𝐾𝐽 + 5 0 𝐾𝐽 )

∆𝐻0 = −906 𝐾𝐽
Thermochemistry
Thermochemistry
 Thermochemistry
Hess’s Law
‘The enthalpy change for a reaction is independent of the way in which a reaction proceeds and
depends only on the initial conditions of the reactants and the final conditions of products’ ‘The
enthalpy change for a reaction is independent of the route taken’

Mathematically it can be expressed as

∆𝐻1 = ∆𝐻2 + ∆𝐻3 = ∆𝐻4 + ∆𝐻5 + ∆𝐻6

 Thermochemistry
Problem

Find the net enthalpy change (∆Hnet) of the reaction below, given the reaction steps and their ∆H values.

Overall reaction: N2H4(l) +H2(g) → 2NH3(g)

(i) N2H4(l) + CH4O(l) → CH2O(g) + N2(g) + 3H2(g) ∆H= – 37kJ/mol

(ii) N2(g) + 3H2(g) → 2NH3(g) ∆H= – 46kJ/mol
(iii) CH4O(l) → CH2O(g) + H2(g) ∆H= – 65kJ/mol

Solution:
Make sure the steps are (a) balanced (b) in the right direction and (c) result in the overall reaction.
The “new” equation steps look like this:
N2H4(l) + CH4O(l) → CH2O(g) + N2(g) + 3H2(g) ∆H= – 37kJ/mol
N2(g) + 3H2(g) → 2NH3(g) ∆H= – 46kJ/mol
CH2O(g) + H2(g) → CH4O(l) ∆H= + 65kJ/mol
With reaction (iii) switched the method of adding all the equations results in the correct overall reaction:

N2H4(l) +H2(g) → 2NH3 (g) ∆H= – 18kJ/mol

 Thermochemistry
Problem
Find the net enthalpy change (∆Hnet) of the reaction below, given the reaction steps and their
∆H values.
Overall Reaction: CS2(l) + 3O2(g) → CO2(g) + 2SO2(g)
(i) C(s) + O2(g) → CO2(g) ∆H= -395 kJ/mol
(ii) S(s) + O2(g) → SO2(g) ∆H= -295 kJ/mol
(iii) C(s) + 2S(s) → CS2(l) ∆H= +90 kJ/mol
Solution:
(i) C(s) + O2(g) → CO2(g) ∆H= -395 kJ/mol
(ii) 2S(s) + 2O2(g) → 2SO2(g) ∆H= -590 kJ/mol
(iii) CS2(l)→ C(s) + 2S(s) ∆H= -90 kJ/mol
With reactions (ii) and (iii) manipulated, the method of adding all the equations results in the
correct overall reaction:

CS2(l) + 3O2(g) → CO2(g) + 2SO2(g) ∆H= -1075 kJ/mol

Thank You