‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬

‫ احمد جياد‬.‫م‬.‫م‬

Thermodynamics
Thermodynamics:the study of the transformations of energy from one form into
another(transformations of energy as heat or work), and its relation to matter.

Thermodynamics terms and basic concepts

An important part of the study of thermodynamics is a few terms and definitions that must be
understood clearly:

System, Boundary, Surroundings:

Thermodynamic system: which is the part of the universe that is being studied that consists
of a number of elements or bodies. It can be small or very large.

Surrounding : The regions outside of the system, essentially the rest of the universe.

A boundary is the actual or notional surface that separates the system from its surrounding

Types of Thermodynamic systems

There are three types of thermodynamic systems depending on the nature of the boundary:

1. Open system: is a system in which both matter and energy can be exchanged with the
surroundings.

Hot water contained in a beaker placed on laboratory table is an open system. The water
vapour (matter) and also heat (energy) is transferred to the surroundings through the
imaginary boundary.

2-Closed system: is a system that can exchange only energy with the surroundings.

A specific quantity of hot water contained in a sealed tube, is an example of a closed system.
While no water vapor can escape from this system, it can transfer heat through the walls of
the tube to the surroundings.
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
3. Isolated system: is a system that can be no exchange energy and matter with the
surroundings.

Let us consider a system 100 ml of water in contact with its vapor in a closed vessel which is
insulated. Since the vessel is sealed, no water vapor (matter) can escape from it. Also,
because the vessel is insulated, no heat (energy) can be exchanged with the surroundings.

-There is another classification of systems according to their homogeneity:

1- Homogeneous system : Homogeneous System A system which consists of a single

phase. Examples : Mixture of air and water vapour, water plus nitric acid .

2- Heterogeneous system: A system which consists of two or more phases. Examples :

Water plus steam, ice plus water.

Phase. A phase is a quantity of matter which is homogeneous throughout in chemical

composition and physical structure.

Properties of a system: Intensive and Extensive properties

The macroscopic or bulk properties of a system (volume, pressure, mass, etc.) can be divided
into two classes:

(a) Intensive properties

(b) Extensive properties

(c ) Specific Properties

Intensive properties do not depend on the quantity of matter present in the system.

Some examples of intensive properties are pressure, temperature, density, and concentration.
If the overall temperature of a glass of water (our system) is 20℃, then any drop of water in
that glass has a temperature of 20℃. Similarly, if the concentration of salt, NaCl, in the glass
of water is 0.1 mole/litre, then any drop of water from the glass also has a salt concentration
of 0.1 mole/litre.

Extensive properties: A property that does depend on the quantity of matter present in the
system. Examples include volume, mass, enthalpy, entropy, and Gibbs’ free energy.

Specific Properties: Extensive properties expressed per unit mass to make them intensive
properties.
𝑒𝑥𝑡𝑒𝑛𝑠𝑖𝑣𝑒 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦
𝑠𝑝𝑒𝑐𝑖𝑓𝑖𝑐 𝑝𝑟𝑜𝑝𝑒𝑟𝑡𝑦 (𝑖𝑛𝑡𝑒𝑛𝑠𝑖𝑣𝑒) →
𝑚𝑎𝑠𝑠
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
Thermal equilibrium describes the condition between two systems where no heat flows
between them when they are connected by a path that can transfer heat. If two systems are in
thermal equilibrium with a third system, then they are in thermal equilibrium with each
other.

Equilibrium states are those states of a system where these macroscopic properties do not
change. The macroscopic properties that define the equilibrium state are called state
functions.

State functions depend only on the initial and final states of a system and are not dependent
on the manner in which the state changed from the initial to the final state. Examples of state
functions are: pressure, temperature, volume, mass, chemical composition, and energy

Therefore, for any state function, X

∆E = Efinal - Einitial

∆P = Pfinal - Pinitial

∆V = Vfinal - Vinitial

∆T = Tfinal - Tinitial

State functions are related to each other by equations of state, mathematical relationships
between state functions that describe the equilibrium state of a system under a given set of
physical conditions. For example, the state functions pressure, temperature, volume, and
amount of an ideal gas (f(p,v,T)=0) are related by the equation of state called the ideal gas
law P =RT/V for one mole.

Thus for attaining a state of thermodynamic equilibrium the following three types of
equilibrium states must be achieved :

1. Thermal equilibrium. The temperature of the system does not change with time and has
same value at all points of the system.

2. Mechanical equilibrium. The pressure in the system is same at all points and does not
change with respect to time.

3. Chemical equilibrium. No chemical reaction takes place in the system and the chemical
composition which is same throughout the system does not vary with time.

Types of thermodynamic processes:

(1) reversible process is defined as a process that can be reversed by inducing infinitesimal
changes to some property of the system, and in so doing leaves no change in either the
system or surroundings.
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
(2) irreversible process is defined as a process that cannot be reversed.

(3) Isothermal Processes :Those processes in which the temperature remains fixed, are
termed isothermal processes.

(4) Adiabatic Processes: Those processes in which no heat can flow into or out of the
system, are called adiabatic processes.

(5) Isobaric Processes:Those processes which take place at constant pressure are called
isobaric processes. For example, heating of water to its boiling point and its vaporization
take place at the same atmospheric pressure.

(6) Isochoric Processes:Those processes in which the volume remains constant are known
as isochoric processes. The heating of a substance in a non-expanding chamber.

(7) 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.

Laws of Thermodynamics

1. Zeroth law of thermodynamics

If two bodies are in thermal equilibrium with a third body, they are in thermal
(thermodynamics) equilibrium with each other.

2. First law of Thermodynamics

the first law can be state as ‘’ Energy can be transferred or transformed but cannot be created
or destroyed”

Heat (q) is defined as the amount of thermal energy transferred from a system to its
surroundings or from one system to another due to the fact that they are at different
temperatures. Heat is measured in units of energy, usually calories or joules. Heat will
always flow from a hotter system to a colder system. Although the process of transferring
heat from one system to another changes the internal energy of both systems, it is not a
property of the state of the system and so is not a state function. Temperature is a measure of
the average thermal energy of a system. When a substance absorbs heat, one of two things
can happen, the temperature of the substance can increase or the substance can undergo a
phase change. In the absence of a phase change, the change in temperature of the substance
is proportional to the amount of heat absorbed. The more heat added, the larger the
temperature change.

Another process that exchanges energy between systems is work.

‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
Work:

Is the transfer of energy by any means other than heat. Physics defines work as the force
required to move an object a certain distance. Work (w) is calculated by multiplying the
force (F) by the distance moved (d), where the force is equal to mass of the object (m)
multiplied by the acceleration (a) of the movement; w = Fd = mad

-Heat(Thermal energy) and work are both processes that transfer energy from one system to
another or from a system to the surroundings. So, they both change the internal energy of a
system.

An important form of work in chemical thermodynamics is accomplished by pressure and

volume changes in the gas phase. This is the kind of work done by the combustion of fuels in
an internal combustion engine, which moves the pistons in the cylinders of an automobile.

W=p∆V

Since energy cannot be created or destroyed, any change in the internal energy of a system
must result in a corresponding change in the energy of the system’s surroundings. The value
of internal energy of a system (E) is a property of the system at equilibrium and is therefore a
state function. The two processes that can change the internal energy of a system are heat
and work and the change in the internal energy (ΔE) of the system is equal to the sum of
these two processe

ΔE = q + w

•q(+) is positive—heat is absorbed by the system.

• q(-) is negative—heat is released from the system

• W(+) is positive—work is done on the system

• W(-) is negative—work is done by the system

If we assume that a certain gas system is in equilibrium, then when this system is supplied
with a certain amount of thermal energy (q joules), Then the state of the system has changed
from the initial equilibrium state to the final equilibrium state If the internal energy of the
system is in final equilibrium state E2, and the internal energy of the system is in initial
equilibrium state E1, then:

∆𝐸 = 𝐸2 − 𝐸1 = 𝑞 + w

𝐸2 = 𝐸1 + 𝑞 + w

Where (E2- E1) represents the difference in the internal energy of the system.
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
q Thermal energy or the amount of heat.

W the work done on the system by the Surrounding .

But if the work is done by the system on the Surrounding, then the work signal is negative
and the equation becomes as follows:

∆𝐸 = 𝑞+(–w) → ∆𝐸 = 𝑞 – w

If the process is exothermic (meaning that the Surrounding is absorbing heat from the
system) then the q-signal is negative

If the process is endothermic (i.e. the system is absorbing heat from the Surrounding) then
the q signal is positive.

Types of processes:

The energy relationship and the state of any system during a process do not depend on the
method of work being done, But it depends on some practical conditions That is reflected in
the system as a whole.

a- Isothermal processes:

The system temperature is constant in these processes, The amount of heat can be added or
lost from the system so that the system keeps its temperature constant, meaning that dT=0.

b- Adiabatic processes

In these processes, there is no exchange in the amount of heat between the system and the
Surrounding ,meaning that q = 0

depending on the first law, the amount of work and internal energy can be calculated for
some processes such as gas expansion and contraction and evaporation processes heating
processes (under constant volume or under constant pressure) and some reactions that result
in gas release.

(1) Expansion against constant pressure:

If a gas has a pressure greater than the external pressure, then the gas, will expand until it is
stopped mechanically or until it is equal internal pressure with external pressure. During this
process, the external pressure (atmospheric pressure)(Pexternal) on the gas remains constant
,Thus, the work done by the system during the expansion From V 1 to V 2 is equal to:-
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
dw=-pexdv
𝑉 𝑉
W=-∫𝑉 2 𝑃𝑒𝑥 𝑑𝑉 = −𝑃𝑒𝑥 ∫𝑉 2 𝑑𝑉
1 1

W= − 𝑃𝑒𝑥 (𝑉2 − 𝑉1)

Thus, the work depends on both the external pressure and the change in volume.

2- Reversible processes:

If we arrange the conditions in such a way that the system is nearly at equilibrium in every
moment, and that, consequently, the direction of the process may be reversed by even a very
slight change of the initial conditions, the process is called reversible or equilibrium. A
reversible process is thus a sequence of (nearly) equilibrium states of a system

The reversible processes are very important because they produce the largest amount of work
that can be obtained from a slight change. As for irreversible processes or non-equilibrium
process (the direction of the process cannot be reversed by any slight change of external
.)conditions, and the process is a sequence of non-equilibrium states

The reversible process occurs slowly and gradually, in contrast to the irreversible process,
which occurs suddenly.

for example The reversible processes are evaporation of water at 100 °C, melting of ice at
0°C, and the chemical reaction at equilibrium:

𝐴+𝐵⇌𝐶+D

As for irreversible processes, such as evaporation of water at 200 °C, melting of snow at

10°C, and reactions accompanied by an explosion.

It is can to calculate the total work done by the system when the volume is changed from V 1
to V2 by relationship

In a reversible expansion : Pgas=Pex

𝑉
W= -∫𝑉 2 𝑃𝑒𝑥 𝑑𝑉
1

Integration can be done and calculate the work in the process of reversible Isothermal
expansion(T constant), after substitution of P from the general equation for ideal gases:

Because Internal energy is function only of temperature, the internal energy of the gas is
unchanged : dE= 0
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
𝑛𝑅𝑇
P=
𝑉

𝑉 𝑛𝑅𝑇 𝑑𝑉
W= = -∫𝑉 2 𝑑𝑉 = −𝑛𝑅𝑇
1 𝑉 𝑉

𝑉2
W= -nRT ln
𝑉1

We can notice from this equation that the system is done more work when the volume
changes,and the temperature increases.

3- Free expansion:

If the amount of external pressure is 0 (Pex=0) , no expansion work is done because the gases
expand into a vacuum This is because there is no external pressure to push the piston.

W=0

From the first law of thermodynamics ∆E = q + w

Therefore, ∆E = q Heat supplied to the system at pressure =0

4- Reactions at constant volume:Isochoric processes

w = −Pex ∆V because of at constant volume ∆V = 0

so, w = 0

∆E=q+w

Therefore, ∆E=qv Heat supplied to the system at constant volume

5- Isobaric processes:( Reactions at constant pressure)

When the reaction takes place at constant pressure there is work done by the system, so the

∆𝐸 = 𝑞 − w

qp = ∆𝐸 + w

Where qp represents thermal energy at constant pressure

Since the work done is equal to:

w = 𝑃 ∆V

qp = ∆𝐸 + 𝑃 ∆V
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
If we assume that the gas is ideal:

qp = ∆𝐸 + ∆𝑛 𝑅T

Examples:

1- What is the change in internal energy of a system that releases 100 J of energy to the
surroundings in the form of heat and has 200 J of work done on it?

Solution:

a. Determine the signs for heat and work. Heat is released from the system so it is negative.
Work is done on the system so it is positive.

b. Substitute the values into the equation for change in internal energy of a system.

ΔE = q + w = -100J + 200J = 100J

2- What is the maximum work that can be obtained from the isothermal, reversible
expansion of a mole of ideal gas at 0°C at its expantion from 2.24 L to 22.4 L?

Solution:
𝑉2
W= -nRT ln
𝑉1

22.4
W= -1×8.314×273 ln
2.24

=− 5227.17 J

3- Calculate the final volume of one mole of an ideal gas initially at 0 oC and 1 atm pressure.
If it absorbs 8368 J of heat during reversible isothermal expansion.

The gas is in the standard temperature and pressure condition i.e. at S.T.P:

Solution:

Hence V1 = 22.4 dm3 and V2 have to be calculated

As given expansion is isothermal and reversible therefore, ∆E = 0

We know that ∆E = q + w
But ∆E = 0
Hence q = – w =- 8368 J
‫المرحلة الثانية‬ ‫قسم الهندسة الكيمياوية‬ ‫كيمياء فيزياوية‬
As work done in reversible isothermal expansion is given by:
w= -nRT ln (V2/ V1)

Therefore nRT ln (V2/ V1) = – w = 8368 J

𝑉2
(1 mol) × (8.314 J K-1 mol-1) × (273 K) ln ( ) = 8368 J
22.4 𝑑𝑚3
V2 = 242.50 dm3

4- In a cyclic process ,heat transfer are +15.7 kJ ,-26.2kJ , -4.86kJ , +31.5kJ .what is the net
work for this process?

Solution:

For cyclic process ∆E=0

∆E= q+w=0

W=15.7-26.2-4.86+31.5=16.14Kj