Physical Chemistry

1. Gases: Description of ideal and real gases.Characteristic physical properties, equations of states, van der Waals equation, virial
equation. Critical state. Kinetic-molecular theory of gases.

Gases
Ideal gases are a theoretical concept that describe gases that follow the gas laws exactly. Real gases, on the other hand, do not
follow the gas laws exactly, and their behavior is influenced by factors such as intermolecular forces and the volume of the gas
molecules.
Characteristic physical properties of gases include pressure, volume, and temperature, which can be related through the ideal gas
law or other equations of state, such as the van der Waals equation or the virial equation. The critical state of a gas is the state at
which it can no longer be condensed into a liquid, and the kinetic-molecular theory of gases explains the behavior of gases based
on the movement of their constituent particles.

From Atkins’

DESCRIPTION OF IDEAL AND REAL GASES

Ideal gas (perfect gas) is a gas that obeys the ideal gas equation, pV = nRT , which is an approximate equation of state of any
gas, and becomes increasingly exact as the pressure of the gas approaches zero.

The ideal gas law works for all ideal gases, regardless of their
chemical identity. But, it is an equation of state that applies only
under certain conditions. It assumes particles participate in perfectly
elastic collisions, have no volume, and don’t interact with each other
except to collide. In other words, the gas behaves according to the kinetic molecular theory of gases.

Properties of an ideal gas:

There are no intermolecular forces between the gas particles.

The volume occupied by the particles is negligible compared to the volume of the container they occupy.

The only interactions between the particles and with the container walls are perfectly elastic collisions

Real gas, an actual gas, behaves more like a perfect gas, the lower the pressure, and is described by the ideal gas equation in the
limit of p → 0.
pV
The gas constant R can be determined by evaluating R = nT
​for a gas in the limit of zero pressure (to guarantee that it is
behaving perfectly). A more accurate value can be obtained by measuring the speed of sound in a low-pressure gas (argon
is used in practice) and extrapolating its value to zero pressure.

Real gases do not obey the perfect gas law exactly. Deviations from the law are particularly important at high
pressures and low temperatures, especially when a gas is on the
point of condensing to liquid.

Physical Chemistry 1
 Additional source: https://sciencenotes.org/real-gas-vs-ideal-gas/
Important: http://vallance.chem.ox.ac.uk/pdfs/PropertiesOfGasesLectureNotes.pdf

CHARACTERISTIC PHYSICAL PROPERTIES and EQUATION OF STATE

The physical state of a sample of a substance, its physical condition, is defined by its physical properties. Two samples of a
substance that have the same physical properties are in the same state. The state of a pure gas can be specified its physical
properties such as:

volume, V

amount of substance (number of moles), n

pressure, p

Physical Chemistry 2
 temperature, T
Note: It has been established experimentally that it is sufficient to specify only three of these variables, for then the fourth variable is
fixed

Each substance is described by an equation of state, which interrelates these four variables. The general form of an equation of
state is: p = f(T , V , n)

VIRIAL EQUATION
There are different ways in which the ideal gas equation may be modified to take account of the intermolecular forces present in a
real gas. One way is to treat the ideal gas as the first term in an expansion of the form:

pVm = RT (1 + B′ p + C ′ p2 + ...)
​

A simple law that is known to be a good first approximation (in this case pV = nRT ) is treated as the first term in a series in
powers of a variable (here, p).

A more convenient form of virial expansion:

B C
pVm = RT (1 + + 2 + ...)
Vm
​

Vm
​

​ ​

These are the two versions of the virial equation of state, which attempts to account for the behavior of real gases. By comparing
to the expression pVm ​ = RTZ , we see that the term in the parentheses can be identified with the compression factor, Z.
The coefficients B,C, ...,which are dependent on the temperature, are the second, third,… virial coefficients.

the first virial coefficient is 1

the third virial coefficient, C, is usually less important than the second coefficient → in a sense that at typical molar
volumes, C/Vm2 ​
<< B/Vm  ​

Virial equation can be used to demonstrate that although the

equation of state of a real gas may coincide with the perfect gas
law as p → 0, not all its properties necessarily coincide with
those of a perfect gas in that limit.

Take for example the value of dZ

dp
 ​ ⇒ the slope of the
graph of compression factor against pressure:
dZ
for a perfect gas, Z = 1and dp
​ = 0(i.e. the slope
of a plot of Z against p is zero) at all pressures

for all real gases, the slope of Z with respect to p

does not necessarily approach 0 (Fig. 1.14),
because several physical properties of gases
depend on derivatives

Physical Chemistry 3
 Because the virial coefficients depend on the temperature,
there may be a temperature at which Z → 1with zero slope at
low pressure or high molar volume (Fig. 1.16)

At this temperature, Boyle temperature, TB  the

​ ⇒
properties of the real gas do coincide with those of a
perfect gas p → 0,

according to the second equation above, Zhas zero slope

as p → 0if B = 0,so we can say that B = 0at the
Boyle temperature

VAN DER WAALS EQUATION

The van der Waals equation of state is a modification of the ideal gas law that accounts for the non-zero volume of gas
molecules and the attractive forces between them.

approximate equation suggested by J.D. van der Waals in 1873

The equation is:

nRT n
p= − a( )2
V − nb
​

V
​

where pis pressure, V is volume, nis the number of moles of gas, Ris the gas constant, T is temperature, aand bare
constants (van der Waals coefficients) for the gas that depend on its properties. These coefficients are characteristic of each
gas but independent of the temperature.

The equation is often written in terms of the molar volume Vm ​ = V

n
​as:

RT a
p= −
V − M − b Vm2
​ ​

The term an2 /V 2 corrects for the attractive forces between gas molecules, and the term nbcorrects for the volume of the gas
molecules themselves.

At low pressures and high temperatures, the van der Waals equation reduces to the ideal gas law, but at high pressures and low
temperatures, the ideal gas law breaks down and the van der Waals equation provides a more accurate description of the
behavior of real gases.

FEATURES OF THE EQUATION

1. Perfect gas isotherms are obtained at high temperatures and large molar volumes.

2. Liquids and gases coexist when cohesive and dispersing effects are in balance.

3. The critical constants are related to the van der Waals coefficients.

CRITICAL STATE
The critical state of a gas is the state at which it can no longer be condensed into a liquid. This state is characterized by the critical
temperature and critical pressure of the gas. At the critical state, the gas has the highest possible density for a gas and exhibits
properties of both a gas and a liquid. The van der Waals equation and other equations of state can be used to predict the critical
state of a gas.

Physical Chemistry 4
 In the context of physical chemistry, the term "critical state" typically refers to the conditions at which a substance undergoes a
phase transition known as the critical point. The critical point is a specific set of temperature and pressure values at which the
distinction between the liquid and gas phases of a substance disappears, and the substance becomes a supercritical fluid.

CRITICAL POINT ⇒ If, however, the compression takes place

at Tc itself, then a surface separating two phases does not
appear and the volumes at each end of the horizontal part of
the isotherm have merged to a single point, the critical point
of the gas.

The temperature, pressure, and molar volume at the

critical point are called the critical temperature, Tc ,​

critical pressure, pc , and critical molar volume, Vc , of

​ ​

the substance.

Collectively, pc , Vc , and Tc are the critical constants of

​ ​ ​

a substance.

Supercritical fluid → the single phase that fills the

entire volume when T > Tc may be much denser than
​

we normally consider typical of gases

KINETIC MOLECULAR THEORY OF GASES

The kinetic-molecular theory of gases is a model that explains the behavior of gases based on the movement of their constituent
particles. According to this theory, gas particles move randomly and independently in all directions and at different speeds. The
collisions between gas particles and with the walls of their container are perfectly elastic, meaning that there is no net loss of kinetic
energy during a collision.
The kinetic energy of a gas is directly proportional to its temperature, and the average kinetic energy of a gas particle is proportional
to the square root of its temperature. This explains why gases at higher temperatures tend to have higher pressures and why the
pressure of a gas decreases as its temperature decreases.
The kinetic-molecular theory also explains why gases are compressible and have low densities compared to liquids and solids. The
volume of gas particles is negligible compared to the volume of their container, and there are no intermolecular forces between gas
particles to hold them together.
In order to apply the kinetic model of gases, the following assumptions are made:

1. The gas consists of molecules of mass, m, in ceaseless random motion.

2. The size of the molecule is negligible, in the sense that their diameters are much smaller than the average distance traveled
between collisions.

3. The molecule interact only through brief, infrequent, and elastic collisions.

Source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_an
2. Thermodynamics: Basic concepts of thermodynamics: the classification of systems and their walls. Laws of thermodynamics.
Heat, work, entropy, enthalpy, free energy. State functions and path functions. Different specific heats, their significance and
determination. Heat engines, refrigerators and heat pumps. Thermochemistry.

CLASSIFICATION OF SYSTEMS AND THEIR WALLS

System → is any three-dimensional region of physical space on which we wish to focus our attention

Physical Chemistry 5
 Surroundings → constitutes to the rest of the physical
universe

Systems can be classified based on their composition

and the types of energy and matter that can flow into or
out of them.

Open systems are systems that can exchange

both matter and energy with their surroundings.
Examples include an open beaker of water, a
human body, or a combustion engine.

Closed systems are systems that can exchange

energy but not matter with their surroundings. The
walls of a closed system are typically impermeable
to matter. Examples include a sealed container of
gas, a refrigerator, or a planet. Isolated systems are systems that cannot exchange
matter or energy with their surroundings. The walls of an
isolated system are completely impermeable. Examples
include the universe as a whole (assuming it is isolated) or
a perfectly insulated container.

Boundary → is the closed three-dimensional surface that encloses the system and separates it from the surroundings. The
boundary may coincide with real physical surfaces: the interface between two phases, the inner or outer surface of the wall of a
flask or other vessel, and so on.

The walls of a system can also be classified based on their permeability to matter and energy.

Diathermal Wall (Conductive Wall) → boundary that allows heat transfer between the system and surroundings. These
walls permit the exchange of heat but not matter.

An example is a metal container that can conduct heat.

Adiabatic Wall (Impermeable to Heat) → boundary that does not allow heat transfer between the system and its
surroundings. This type of wall is perfectly insulated and does not permit the flow of thermal energy across it. It can,
however, allow for the exchange of matter.

An example is a thermally insulated container.

Permeable Wall (Allows Matter Exchange) → boundary that allows for the transfer of matter (substances) between the
system and its surroundings. Such walls can permit the passage of molecules, atoms, or other chemical species while
maintaining the conservation of energy.

An example is a porous membrane that allows the flow of gases but not heat.

INTENSIVE AND EXTENSIVE PROPERTIES OF THE SYSTEM

Intensive → the same, boiling point, density, state of matter, color, melting point, odor,
irrespective of the size of temperature, refractive index, luster, hardness, ductility, malleability,
the system conductivity, pressure, concentration, viscosity, surface tension

Extensive → changes, volume (in gases), mass, size, weight, length, width, surface area,
when the system is twice internal energy, enthalpy, entropy, Helmholtz free energy, Gibbs free
as big energy, moles, heat capacity

LAWS OF THERMODYNAMICS

Physical Chemistry 6
 Zeroth Law of Thermodynamics

states that if two systems are in thermodynamic

equilibrium with a third system, the two original systems
are in thermodynamic equilibrium with each other. This
law is the basis for the concept of temperature and is
often used to define temperature scales.

First Law of Thermodynamics

states that energy cannot be created or destroyed, only transferred or converted from one form to another. This law is often
referred to as the law of conservation of energy and is the basis for the concept of internal energy.

states that the internal energy of an isolated system is constant, ΔU = q + w

Second Law of Thermodynamics

in terms of entropy: states that the entropy of an isolated system increases in the course of a spontaneous change,
ΔStot > 0
​

The second law places limits on the efficiency of engines and other energy conversion devices.

Third Law of Thermodynamics

states that the entropy of all perfect crystalline substances is zero at T = 0.This law is used to define the thermodynamic
entropy scale.

Source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_an

Heat, work, entropy, enthalpy, free energy

Heat
Heat is a form of energy that is transferred between two systems by virtue of a temperature difference between them. The transfer of
heat is a process that can occur spontaneously, from a hotter system to a colder system, and is governed by the laws of
thermodynamics.

Work
Work is a form of energy transfer that occurs when a force is applied to an object and it undergoes displacement. Work can be done
on a system to increase its internal energy, or it can be done by a system as it performs mechanical work on its surroundings.

Physical Chemistry 7
 Entropy
Entropy is a measure of the degree of disorder or randomness in a system. The second law of thermodynamics states that the
entropy of an isolated system will tend to increase over time, as energy is transferred from hotter to cooler objects and the system
moves toward a state of increasing disorder.
dqrev
The thermodynamic definition of entropy is dS = T . The statistical definition is given by Boltzmann formula,
​

​
S=
k ln W .
C
The entropy of a substance is measured from the area under a graph of Tp against T, using the Debye extrapolation at low
​

temperatures, Cp = aT 3 as T → 0.

​

Enthalpy
Enthalpy is a thermodynamic property that describes the total heat content of a system. It is equal to the internal energy of the
system plus the product of pressure and volume, H = U + pV .
The enthalpy change is the energy transferred as heat at constant pressure, ΔH = qp 
​

Free Energy
Free energy is a measure of the amount of work that can be done by a system during a spontaneous process. It is defined as the
difference between the enthalpy and the product of the temperature and the entropy of the system.

State functions and path functions

In thermodynamics, a state function is a property of a system that depends only on the current state of the system, not on how the
system arrived at that state. Examples of state functions include temperature, pressure, and internal energy. State functions are
often represented using capital letters, such as U for internal energy or H for enthalpy.
In contrast, a path function is a property of a system that depends on the path taken to get to a particular state. Examples of path
functions include work and heat. Path functions are often represented using lowercase letters, such as q for heat and w for work.

Different specific heats, their significance and determination

Specific heat is a measure of the amount of heat required to raise the temperature of a substance by a certain amount. There are
two types of specific heat: specific heat at constant volume, (Cv ) and specific heat at constant pressure (Cp ). These values
​ ​

are important in thermodynamics because they describe the amount of heat required to change the temperature and state of a
substance.

Specific heat at constant volume is the amount of heat Specific heat at constant pressure is the amount of heat
required to raise the temperature of a substance by 1 required to raise the temperature of a substance by 1
degree Celsius while keeping its volume constant. degree Celsius while keeping its pressure constant.

can be determined using a bomb calorimeter, which can be determined using a calorimeter with a pressure-
measures the heat released or absorbed during a release mechanism, which measures the heat released
chemical reaction at constant volume. or absorbed during a reaction at constant pressure.

qv = Cv ΔT
​ ​ pΔV = RΔT

The ratio of specific heat at constant pressure to specific heat The specific heats of a substance can also be calculated using
at constant volume, denoted by γ , which describes the theoretical models, such as the Debye model for solids or the
behavior of a gas when it is compressed or expanded. For an equipartition theorem for gases. These models use the
ideal gas, γ is a constant that depends only on the number of properties of the substance, such as its atomic or molecular
degrees of freedom of the gas molecules. structure, to predict its specific heats.

Cp
γ=
​

Cv ​

Additional source: https://www.grc.nasa.gov/www/k-

12/airplane/specheat.html

Physical Chemistry 8
 Heat engines, refrigerators and heat pumps
Heat engines are devices that convert thermal energy into mechanical work. There are several types of heat engines, but they are
characterized by the following:

1. They all receive heat from a high-temperature source (oil furnace, nuclear reactor, etc.).

2. They convert part of this heat to work (such as turning a turbine).

3. They expel the remaining heat to a lower-temperature sink (such as the atmospheres).

4. They operate in a cycle.

Examples of heat engines include steam engines, gasoline engines, and diesel engines.

Efficiency: The efficiency of a heat engine is defined as the

ratio of the work output to the heat input. It is described by the
Carnot efficiency, which depends on the temperatures of the
hot and cold reservoirs.

Carnot cycle → theoretical cycle that describes the

maximum efficiency that can be achieved by a heat
engine operating between two temperatures.

The efficiency of a real engine is always less than the

efficiency of a Carnot engine operating between the
same two temperatures.

Refrigerators:

designed to remove heat from a low-temperature environment (the interior of the refrigerator) and reject it to a higher-
temperature environment (the room or outside)

typically consists of a refrigeration cycle that includes a compressor, condenser, expansion valve, and evaporator

a working fluid (refrigerant) circulates through these components to transfer heat from the interior to the exterior

Refrigerators work by compressing the refrigerant, causing it to release heat (condense) outside the refrigerator.

Then, the refrigerant expands inside the refrigerator, absorbing heat (evaporates) from the interior, thus cooling the
contents.

Heat pumps:

it is similar to a refrigerator but it operates in reverse

Physical Chemistry 9
 designed to transfer heat from a low-temperature environment (e.g., the outside air or ground) to a higher-temperature
environment (e.g., the interior of a building)

use a refrigeration cycle similar to that of a refrigerator but can reverse the direction of heat transfer to provide both heating
and cooling functions.

In heating mode, a heat pump absorbs heat from a low-temperature source (e.g., outdoor air) and releases it inside the
building.

In cooling mode, it absorbs heat from the interior and releases it outside, providing cooling.

Sources: https://www.sfu.ca/~mbahrami/ENSC 388/Notes/Second Law of Thermodynamics.pdf

https://www.lehman.edu/faculty/anchordoqui/SJ4.pdf

THERMOCHEMISTRY
Thermodynamics → study of energy and its transformations

Thermochemistry → is the study of the energy transferred as heat during the course of chemical reactions

branch of thermodynamics because a reaction vessel and its contents form a system, and chemical reactions result in the
exchange of energy between the system and the surroundings

Key Concepts:

Physical Chemistry 10
 1. Calorimetry → can be used to measure the energy supplied or discarded as heat by a reaction, and can identify q with a
change in internal energy (if the reaction occurs at constant volume) or a change in enthalpy (if the reaction occurs at
constant pressure). Conversely, if we know ∆U or ∆H for a reaction, we can predict the energy (transferred as heat) the
reaction can produce.

Calorimeter → apparatus that measures heat flow

calorie is a unit of measure equal the amount of heat required to raise the temperature of 1 gram of water by 1 degree
Celsius

Heat capacity → amount of energy required to raise the temperature of a given object by 1°C

Molar heat capacity → when referring to pure substances; heat capacity of 1 mol of substance
q
Specific heat → heat capacity of 1 g of a substance (as opposed to a mole); C = mΔT

​

2. Heat → form of energy which can easily transfer to or from a system, the result of which
is a temperature difference between the system and its surroundings

endothermic → when heat is absorbed from the surroundings

exothermic → when a system releases heat to its surroundings

3. Standard enthalpy changes

standard enthalpy change, ΔH θ , the change in enthalpy for a process in which the initial and final substances are in
their standard states

the standard state of a substance at a specified temperature is its pure form at

1 bar.

a. Enthalpies of physical change

Standard enthalpy of transition, Δtrs H θ → standard enthalpy change that accompanies a change of physical
​

state

standard enthalpy of vaporization, Δvap H θ → represents the amount of heat energy required to vaporize
​

one mole of a substance at its boiling point under standard conditions of temperature and pressure (STP)

standard enthalpy of fusion, Δf us H θ → the standard enthalpy change accompanying the conversion of a
​

solid to a liquid

b. Enthalpies of chemical change

There are two ways of reporting the change in enthalpy that accompanies a chemical reaction:

Thermochemical equation → a combination of a chemical equation and the corresponding change in standard
enthalpy:

Alternatively, we write the chemical equation and then report the standard reaction enthalpy, Δr H θ 
​

standard enthalpy of combustion, Δc H θ → the standard reaction enthalpy for the complete oxidation of an
​

organic compound to CO2 gas and liquid H2 O if the compound contains C, H, and O, and to N2 gas if N is
​ ​ ​

also present

c. Hess’s Law

this is the application of the First Law, and states that: the standard enthalpy of an overall reaction is the sum of
the standard enthalpies of the individual reactions into which a reaction may be divided

Physical Chemistry 11
 4. Standard enthalpies of formation

standard enthalpy of formation, Δf H θ → standard reaction enthalpy fro the formation of the compound from its elements in
their reference states

reference state of an element → is its most stable state at the specified temperature and 1 bar

a. the reaction enthalpy in terms of enthalpies of formation

the value of Δr H θ for the overall reaction is the sum of these “unforming” and forming enthalpies. Because “unforming”
​

is the reverse of forming, the enthalpy of an unforming step is the negative of the enthalpy of formation

b. Enthalpies of formation and molecular modelling

a. Can we construct standard enthalpies of formation from a knowledge of the chemical constitution of the species? The
short answer is that there is no thermodynamically exact way of expressing enthalpies of formation in terms of
contributions from individual atoms and bonds

In the past, approximate procedures based on mean bond enthalpies , ΔH(A − B),→ the average enthalpy
change associated with the breaking of a specific A-B bond, have been used:

A − B(g) → A(g) + B(g) ΔH(A − B)

5. the temperature-dependence of reaction enthalpies

the temperature dependence of the reaction enthalpy is given by the Kirchhoff’s law:

It is normally a good approximation to assume that Δr Cp is independent of the temperature, at least over reasonably
​ ​

limited ranges

3. Phase equilibria: Phase rule and its concepts. Characterization of phase transitions, phase diagrams and phase equilibria.
Phase transitions in one-component and multicomponent systems.

PHASE RULE AND ITS CONCEPTS

Phase rule → aka Gibbs phase rule, is a fundamental concept in physical chemistry that helps describe and predict the equilibrium
conditions of a system involving multiple phase (e.g., solids, liquids, and gases) and components (chemical species)

it is a general relation between the variance, F, the number of components, C, and the number of phases at equilibrium, P,
for a system of any composition:

F =C −P +2

KEY CONCEPTS:

Degrees of Freedom (F) → a variable that can be changed independently without changing the number of phases in the
system. For example, the temperature, pressure, and composition of a system are degrees of freedom.

Components (C) → are the chemical species or types of substances present in the system. Each component can vary in
concentration independently.

Phases (P) → are physically distinct regions within a system where the properties are uniform. Common phases include
solids, liquids, and gases.

Physical Chemistry 12
 CHARACTERIZATION OF PHASE TRANSITIONS, PHASE DIAGRAMS, PHASE EQUILIBRIA
Phase transition → is a change in the physical state of a
substance, such as melting, freezing, boiling, or condensing.
Phase transitions can be characterized by changes in
temperature and pressure, as well as changes in other
thermodynamic properties such as entropy and enthalpy.

Solid to Liquid (Melting): occurs when a solid substance

is heated, causing its particles to gain enough energy to
break their ordered arrangement and become a disordered
liquid.

Liquid to Gas (Vaporization): When a liquid is heated to a

certain temperature, it transitions into a gas as the kinetic
energy of the particles overcomes intermolecular forces.

Solid to Gas (Sublimation): Some substances can

transition directly from a solid to a gas without passing
through the liquid phase. This is called sublimation.

Gas to Liquid (Condensation): The reverse of

vaporization, where a gas loses energy and transitions into
a liquid.

Liquid to Solid (Freezing): When a liquid loses enough

energy (usually by cooling), its particles form an ordered,
solid structure.

Gas to Solid (Deposition): The reverse of sublimation,

where a gas transitions directly into a solid.

Phase diagrams → are graphical representations of the phase

behavior of a substance as a function of temperature, pressure,
and composition. Phase diagrams can be used to predict the
conditions under which a substance will exist in different
phases, and to determine the properties of those phases.
Key features:

Triple Point: The temperature and pressure conditions

at which all three phases coexist in equilibrium.

Critical Point: The temperature and pressure beyond

which a distinct liquid and gas phase no longer exist;
instead, there is a continuous phase transition.

Phase Regions: Areas within the diagram where a

specific phase is stable under given conditions.

Phase Boundaries: Lines on the diagram separating

regions where different phases are stable. For example, the
line separating the liquid and gas phases is the vapor-liquid
equilibrium line.

Physical Chemistry 13
 Phase equilibria → refers to the conditions under which two or
more phases of a substance coexist in thermodynamic
equilibrium. Phase equilibria can be characterized using phase
diagrams, which show the boundaries between regions of
different phases.
There are several types of phase equilibria:

Vapor-Liquid Equilibrium (VLE): This occurs when a

liquid and its vapor phase coexist in equilibrium, as seen in
the phase boundary between the liquid and gas regions in
a phase diagram.

Solid-Liquid Equilibrium (SLE): In this case, a solid and a

liquid phase coexist in equilibrium. This equilibrium is
important in processes like freezing and melting.

Solid-Gas Equilibrium (SGE): It involves the coexistence

of a solid and a gas phase. Sublimation and deposition are
examples of SGE.

Triple-Point Equilibrium: At the triple point, all three

phases (solid, liquid, and gas) coexist in equilibrium, and it
is a unique point on a phase diagram.

PHASE TRANSITION IN ONE-COMPONENT SYSTEM

In one-component systems, phase diagrams are typically two-dimensional plots of temperature vs. pressure, with lines
representing the boundaries between regions of different phases. The most common types of phase transitions in one-component
systems are melting, boiling, and sublimation.
Examples of one-component systems:

Physical Chemistry 14
 Source: https://colloidmueg.weebly.com/uploads/2/5/7/3/25736627/lect3_phase.pdf
Additional: http://www.physics.rutgers.edu/~gersh/351/Lecture 16.pdf

PHASE TRANSITION IN MULTI-COMPONENT SYSTEMS

In multi-component systems, phase diagrams are typically three-dimensional plots of temperature, pressure, and composition,
with surfaces representing the boundaries between regions of different phases. Multi-component phase diagrams can be much
more complex than those of one-component systems, due to the larger number of degrees of freedom.

Key concepts:

Multi-component Phase Diagrams → Phase diagrams for multi-component systems are more complex than those for one-
component systems. They often involve multiple phases in equilibrium, including solid solutions, liquid mixtures, and gas
mixtures. These diagrams help visualize how phase compositions change with variations in temperature and pressure.

Solid solutions → Multi-component systems often form solid solutions, where different elements or compounds are
incorporated into the crystal lattice of a solid. The composition of solid solutions can vary continuously within certain limits.

Eutectic and Peritectic Reactions → Eutectic and peritectic reactions are common in multicomponent phase transitions.
Eutectic reactions involve the simultaneous solidification of two or more phases from a liquid, while peritectic reactions
involve the transformation of one solid phase into another with the presence of a liquid phase.

Binary Phase Diagrams → involve two components, are commonly used to study multi-component systems. They provide
valuable insights into how phase transitions occur in mixtures of two different substances.

Example: Binary Phase Diagram of toluene and benzene

Physical Chemistry 15
 Additional source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/DeVoes_Thermodynamics_and_Chem
Additional source: https://ocw.mit.edu/courses/3-012-fundamentals-of-materials-science-fall-
2005/9fa239d16926f0de29a87ed6f2e963d0_lec19t.pdf
4. Chemical equilibrium: The free energy profile of chemical reactions. Chemical potential. Characterization of chemical equilibria,
various types of reaction quotients and equilibrium constants. External influences on equilibria. Equilibria in chemical systems.

FREE ENERGY PROFILE OF CHEMICAL REACTIONS

The free energy profile (FE Profile) of a chemical reaction describes the change in free energy (G) of the system as the reaction
proceeds from reactants to products.

The profile typically includes an energy barrier, corresponding to the activation energy required to initiate the reaction, and
the free energy change associated with the reaction.

The magnitude of the free energy change is related to the equilibrium constant of the reaction, with larger values of K
corresponding to more favorable reactions.

External factors such as temperature, pressure, and concentration can affect the free energy profile and therefore the
equilibrium constant of the reaction.

Key concepts:

Gibbs free energy (G) of a system → is a measure of the amount of usable energy (energy that can do work) in that
system.

change in Gibbs free energy: ΔG = Gf inal − Ginitial 

​ ​

extent of a reaction (ξ)→ the change in the number of moles of reactants or products, divided by their respective
stoichiometric coefficients, as the reaction progresses from its initial state to a given point in time

reaction Gibbs energy, Δr G→ defined as the slope of the graph of the Gibbs energy plotted against the extent of reaction
​

Physical Chemistry 16
 relationship of Gibbs free energy, enthalpy, and entropy

spontaneous reactions → reactions with a negative ΔGrelease energy, which means that they can proceed without
an energy input

when a reaction releases heat (negative ΔH ) or increases the entropy of the system → make ΔGmore negative

non-spontaneous reactions → reactions with a positive ΔGneed an energy input in order to take place

when a reaction absorbs heat or decreases the entropy of the system → make ΔGmore positive

Exergonic and endergonic reactions: We can express the spontaneity of a reaction at constant temperature and pressure
in terms of the reaction Gibbs energy:

exergonic (work producing) → a reaction for which Δr G ​ < 0

because the process is spontaneous, it can be used to drive another process, such as another reaction, or used to
do non-expansion work

endergonic (work consuming) → a reaction for which Δr G ​

> 0
the reaction can be made to occur only by doing work on it, such as electrolysing water to reverse its spontaneous
formation reaction

Reactions at equilibrium are spontaneous in neither direction: they are neither exergonic nor endergonic.

Activation energy (Ea) → the energy barrier that must be overcome for a reaction to proceed from reactants to products. It
is determined by the energy of the transition state and affects the rate of the reaction. Higher Ea values indicate slower
reactions.

Physical Chemistry 17
 Reaction coordinate → The x-axis of the graph represents the reaction coordinate, which is a measure of the progress of
the reaction from reactants to products. It is often depicted as a simple linear coordinate, but it can also be more complex in
some cases.

Energy axis → the y-axis represents the Gibbs free energy change (ΔG) for the reaction

Additional source: https://www.khanacademy.org/science/biology/energy-and-enzymes/free-energy-tutorial/a/gibbs-free-energy

CHEMICAL POTENTIAL
Chemical potential is a thermodynamic quantity that describes the potential energy of a molecule to undergo a change in its
chemical composition.

defined as the partial derivative of the Gibbs free energy with respect to the number of molecules of a particular species,
while holding all other variables constant

Chemical potential is important in understanding chemical equilibria, and it can be used to determine the direction of
spontaneous chemical reactions.

In essence, it represents the driving force for chemical reactions to occur.

CHEMICAL EQUILIBRIA
Chemical equilibrium refers to the state of a chemical reaction when the rates of the forward and reverse reactions are equal, and
the concentrations of reactants and products remain constant over time.

The equilibrium state is characterized by the equilibrium constant, which relates the concentrations of the reactants and
products at equilibrium:

[C]c [D]d
Kc =
[A]a [B]b
​ ​

where a, b, c, and d are the stoichiometric coefficients of the reactants and products.

The value of Kc tells us whether the reactants or products are favored at equilibrium.

If Kc ​ > 1 ⇒ the products are favored;

Physical Chemistry 18
 if Kc ⇒ the reactants are favored; and
< 1
if Kc = 1⇒ the reactants and products are present in equal amounts.

REACTION QUOTIENTS
Reaction quotients are used to describe the state of a
chemical reaction that is not at equilibrium. The reaction
quotient, Qc, is defined in the same way as the equilibrium
constant, but with the concentrations of the reactants and
products at any given time:

[C]c [D]d
Qc =
[A]a [B]b
​ ​

⇒
If Qc > Kc favors the reactants (forward reaction)
and the reaction will shift to the left to reach equilibrium

⇒
If Qc < Kc favors the products (reverse or
backward reaction) and the reaction will shift to the right
to reach equilibrium

If Qc = Kc ⇒ the system is at equilibrium.

Note: The main difference between K and Q is that K describes
a reaction that is at equilibrium, whereas Q describes a reaction
that is not at equilibrium.

TYPES OF REACTION QUOTIENTS:

The most common types:

⇒
Concentration quotient (Qc ) used for reactions in
​

which the concentrations of reactants and products are

expressed in terms of molarity (moles per liter)

measures aqueous or gaseous concentration at a

particular moment

calculated in the same way as the equilibrium

constant (Kc ), using the concentrations of the
​

species involved in the reaction at a particular point

in time

Pressure quotient (Qp ) ​ ⇒ used for reactions involving

gases

measures gaseous partial pressure at a particular

moment

calculated in a manner similar to Qc, but the

concentrations are replaced with partial pressures

Physical Chemistry 19
 Other types:

⇒
Solubility Product Quotient (Qsp ) used for reactions involving the dissolution of sparingly soluble salts in water. It is
​

calculated by using the concentrations of ions in solution, just like Qc, but for dissolution reactions.

Reaction quotient for Redox Reactions (Q) ⇒ the reaction quotient, Q, is used to determine the spontaneity of the
reaction. It is calculated based on the concentrations (or activities) of the reactants and products involved in the redox
reaction.

Types of equilibrium constants:

Common types:

⇒ relates the concentrations of the reactants and products at equilibrium.

Equilibrium constant (Kc ) ​

Homogeneous equilibrium constant (Kp )⇒ relates the pressures of the reactants and products at equilibrium in a gas-
​

phase reaction.

Heterogeneous equilibrium constant (K) ⇒ relates the concentrations of the reactants and products at equilibrium in a
reaction involving a solid or liquid phase.

Other types:

Ionic product for water (Kw ) ​

⇒ special equilibrium constant for the autoionization of water.
represents the equilibrium constant for the reaction of water molecules ionizing into hydronium ions (H3O+) and
hydroxide ions (OH-).

temperature-dependent and is typically used in the context of acid-base chemistry and pH calculations.

Solubility Product constant (Ksp) ⇒ used for sparingly soluble salts and represents the equilibrium constant for the
dissolution of an ionic compound in water. It describes the extent to which the compound will dissolve in water and is related
to the concentrations of its ions in solution.

Acid Dissociation Constant (Ka ) ​ ⇒ used for weak acids and represents the equilibrium constant for the dissociation of
the acid in water, producing hydronium ions (H3O+). It is a measure of the acid's strength.

binding constants, association constants, dissociation constants, stability constants, and formation constants

Sources: https://www.thoughtco.com/definition-of-equilibrium-constant-605099
https://alevelchemistry.co.uk/definition/equilibrium-constant/

EXTERNAL INFLUENCES ON EQUILIBRIA

Equilibria respond to changes in pressure, temperature, and concentrations of reactants and products. The equilibrium constant
for a reaction is not affected by the presence of a catalyst or an enzyme (a biological catalyst).
The outcome is governed by the Le Chatelier's principle, which states that:

A system at equilibrium, when subjected to a disturbance, responds in a way that tends to minimize the effect of the
disturbance.

Physical Chemistry 20
 Key concepts:

a. Effect of concentration

If concentration of one species changes, concentration of other species CHANGES to keep the value of K the same (at
constant K)

no change in K → only position of equilibrium changes

ADDING PRODUCTS → equilibrium shifts to reactants

ADDING REACTANTS → equilibrium shifts to products

An increase in the concentration of a reactant will shift the equilibrium to favor the product(s), and an increase in the
concentration of a product will shift the equilibrium to favor the reactant(s).

b. Effect of pressure (gas equilibrium)

Increase P in the system by reducing the volume

Increasing P shifts equilibrium to side with fewer molecules (to try to reduce P

An increase in pressure will shift the equilibrium to favor the side with fewer moles of gas, and a decrease in pressure
will shift the equilibrium to favor the side with more moles of gas.

c. Effect of temperature

Exothermic reactions ⇒ increased temperature favors the reactants

Physical Chemistry 21
 Endothermic reactions ⇒ increased temperature favors the products
An increase in temperature will shift the equilibrium in favor of the endothermic reaction (the reaction that absorbs heat),
and a decrease in temperature will shift the equilibrium in favor of the exothermic reaction (the reaction that releases
heat).

The temperature dependence of the equilibrium constant is given by the van’t Hoff equation:

K Δ Hθ
= r 2
​

d ln
dT
​

RT
​

van’t Hoff equation ⇒ is an expression for the slope of a plot of the equilibrium constant (specifically, ln K) as a
function of temperature

a negative slope means that ln K, ad therefore K itself, decreases as the temperature rises

in the case of an exothermic reaction, the equilibrium shifts away from the products

to calculate K at one temperature in terms of its value at another temperature, and provided Δr H θ is independent
​

of temperature, we use

Δr H θ 1 1
ln K2 − ln K1 = −( )( − )
​

​ ​ ​ ​ ​

R T2 T1 ​ ​

d. Effect of catalyst

adding a catalyst → no change in K

a catalyst only affects the RATE of approach to equilibrium

Sources: https://www.chemistry.mcmaster.ca/~aph/chem1a3/lectures/lec08/sld039.htm
https://www.tsfx.edu.au/resources/N_-_Uni_of_North_Florida_-_2046chapter15.pdf

https://web.lemoyne.edu/~giunta/LeChatelier1888.pdf

Physical Chemistry 22
 EQUILIBRIA IN CHEMICAL SYSTEMS
Static equilibria

A static equilibrium is a state reached when a reaction

goes to completion. At this stage, the rates of forward
and reverse reaction both equal zero.

can occur in two situations:

When all reagents or the limiting reagent have

been consumed and converted into products.

When the activation energy of a reaction is too

large to overcome
under a particular setting e.g. temperature or
pressure is too low. The movement between
molecules/particles is too slow to overcome this
energy.

there are no dynamic forces acting on the reactants nor

the products.
As a result, at the point of equilibrium the reaction
practically stops and there are no movements between
reactants and products. Thus a reaction which has reached
a static equilibrium is said to be irreversible.

Dynamic equilibria

Reactants and products which are in dynamic equilibrium are acted

upon by dynamic forces so there are movements between reactants
and products. However, the rates of forward and reverse reaction are
equal.

In a closed system, any reversible reaction will reach a state of

equilibrium. At this point, there is no macroscopic change as the overall
concentrations of reactants and products stay the same.

At a microscopic or molecular level, reactants and products are

charging into one another at the same rate. A dynamic equilibrium exists
in a reaction when rates of forward and backward reactions equal and The change in Gibbs free energy for both
are non-zero in value. the forward and reverse reactions at
equilibria is zero (ΔG=0). The means the
forward and reverse reactions are equally
as spontaneous.

Source: https://scienceready.com.au/pages/introduction-to-equilibria
5. Transport processes: Diffusion, thermal conduction, viscosity. Fick’s laws. The Einstein equation, Nernst–Einstein and Stokes–
Einstein equation for calculating diffusion coefficients.

DIFFUSION, THERMAL CONDUCTION, VISCOSITY

Physical Chemistry 23
 Diffusion → is a process that involves the random motion of
particles through space, usually due to a concentration gradient
dc
dx
​in the system

molecules move from an area of high concentration to

an area of low concentration

the diffusion coefficient (D)→ is a measure of the

mass solute transported in a given period of time under
the influence of a known driving force; SI units (m2 s−1 )

the driving force is essentially the concentration

gradient caused by external forces, such as:
gravitational field or centrifugal field.

Source: https://sci-
hub.se/https://doi.org/10.1002/0471623571.ch10

https://biologyreader.com/examples-of-diffusion-in-daily-
life.html
two kinds of diffusion: translational and rotational

Examples:

A tea bag immersed in a cup of hot water will diffuse

into the water and change its colour.

A spray of perfume or room freshener will get diffused

into the air by which we can sense the odour.

Thermal conduction → is the migration of energy down a

temperature gradient

it is the transfer of heat through a material or between

materials in contact with it

occurs due to the random motion of molecules and the

transfer of energy from higher to lower temperature
regions.

the rate of thermal (the flux of the energy associated

with thermal motion) is found to be proportional to the
temperature gradient:
The coefficient of thermal conductivity (λ)is defined by
dT Fourier’s Law:
J (energy) ∝
dz
​

SI unit of flux: (J m−2 s−1 ) dT (z)

JE = −κ
A positive value of J signifies a flux towards positive z; a
​

dz
​

negative value of J signifies a fluz towards negative z

Examples:

the handle of a hot pan heating up,

a metal spoon left in a cup of hot tea becoming hot to

the touch

a metal roof becoming hot on a sunny day

Source: https://homepage.univie.ac.at/franz.vesely/sp_english/sp/node10.html

Physical Chemistry 24
 Viscosity → is the migration of linear momentum down a
velocity gradient and the flux of momentum is proportional to
the velocity gradient

to see the connection between the flux of momentum

and the viscosity, consider a fluid in a state of Newton
flow → which can be imagined as occurring by a series
of layers moving past one another (Fig. 21.11)

the flux of the x-component of momentum is

proportional to dv
dz , because there is no net flux when
x
​

all the layers move at the same velocity:

dvx
J (x − comp) = −η
​

dz
​

the constant of proportionality, η → is the coefficient

of viscosity

units: kg m−1 s−1 ; poise (P) where P =

10−1 kg m−1 s−1 
Viscosity is the quantity that describes a fluid’s
resistance to flow..

At a molecular level, viscosity is a result of the interaction

between the different molecules in a fluid. This is also
understood as friction between the energy required to make
a fluid flow.

FICK’S LAW
Fick's laws → describe the diffusion of a solute in a solvent and the flux of the solute through a medium. They state that the flux of
the solute is proportional to the gradient of the solute concentration.

a. Fick’s First Law of Diffusion → states that the flux of the equation indicates that if the flux and the change in
matter is proportional to the concentration gradient. It can concentration over time are known, then the diffusion
be expressed as: coefficient can be calculated

dc the first law can only be applied to systems in which the

J m = −D
dx
​

conditions remain the same ⇒ if the flux coming into the

system equals the flux going out
the negative sign indicates that the concentration
gradient is negative

Physical Chemistry 25
 similarly, it describes the change of concentration with time
b. Fick’s Second Law of Diffusion → states that the rate of
and expressed as:
change in concentration at a point in space is proportional
to the second derivative of concentration with space
dc d2 c
=D 2
Fick’s second law is more applicable to physical dt
​

dx
​

science and other systems that are changing. This

where dc represents the rate of change of
second law is applied to systems in which the condition dt
​

d2 c
are not steady, or the solution in not equal throughout. concentration in a certain area and dx 2 represents the
​

changes that the change in concentration can take; this

Source: would not be a smooth curve
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physica
This term accounts for a varying concentration in the
system. If the concentration does not vary, then:

d2 c
=0
dx2
​

Einstein equation for calculating diffusion coefficient

Einstein equation: The Einstein equation relates the diffusion The Einstein-relation between the diffusion coefficient and
coefficient of a solute to its molecular size and the viscosity of the ionic mobility is:
the solvent.
μRT
D= ​

zF

Nernst-Einstein equation for calculating diffusion coefficient

Nernst-Einstein equation: The Nernst-Einstein equation relates the diffusion coefficient of an ion in a solution to the ion's charge,
the temperature of the solution, and the viscosity of the solution.

the Einstein relation provides a link between the molar conductivity of an electrolyte and the diffusion coefficients of its ions.
First, we write for each type of ions:

z 2 DF 2
λ = zuF =
RT
​

Then, from the Λ°m = ν+ λ+ + ν− λ− , the limiting molar conductivity is given below, which is the Nernst-Einstein
​ ​ ​ ​

equation:

2 2 F2
Λm = (ν+ z+​D+ + ν− z−
​ ​ D− ) ​ ​ ​ ​

RT
one application of this equation is the determination of of ionic diffusion coefficients from conductivity measurements and
another us to predict the conductivities using model of ionic diffusion

Stokes-Einstein equation for calculating diffusion coefficient

Stokes-Einstein equation: The Stokes-Einstein equation relates the diffusion coefficient of a particle in a fluid to the particle's size,
the viscosity of the fluid, and the temperature of the fluid.

Stokes-Einstein equation → relates the diffusion coefficient to the frictional force:

kT
D=
f
​

If the frictional force is described by Stokes’ law, then we also obtain a relation between the diffusion coefficient and the
viscosity of the medium:

kT

Physical Chemistry 26
 kT
D=
6πηa
​

these two equations make no reference to the charge of the diffusing species

therefore, the equation also applies in the limit of vanishingly small charge, that is, it also applies to neutral molecules
6. Fundamental of reaction kinetics: The concepts of reaction rate and rate law. Thermal activation and the temperature
dependence of the rate coefficient. The information content of the activation energy and the pre-exponential factor.

CONCEPTS OF REACTION RATE AND RATE LAW

Reaction rate is defined as the change in concentration of reactants or products per unit time. It is a measure of how quickly a
reaction is occurring.

reaction rates depend on the composition and the temperature of the reaction mixture

usually expressed in molarity/time in seconds (M/s)

can be defined in terms of two observables:

the rate of consumption → reactants are consumed and their concentrations go down

the rate of formation of products → rate at which the products are formed and so their concentrations go up

Source:
https://chem.libretexts.org/Courses/University_of_Arkansas_Little_Rock/Chem_1403%3A_General_Chemistry_2/Text/14%3A_Rates

Rate law shows how the rate of a chemical reaction depends on reactant concentration.

more formally, it is an equation that expresses the rate of reaction as a function of the concentrations of all the species
present in the overall chemical equation for the reaction at some time

and is typically expressed as:

rate = k[A]m [B]n

where k is the rate constant and m and n are the reaction orders with respect to reactants A and B, respectively.

the rate constant is independent of the concentrations but depends on the temperature

Determination of the rate law

a. the determination of a rate law is simplified by the isolation method → in which the concentration of all the reactants
except one are in large excess

If B is in large excess, for example, then to a good approximation its concentration is constant throughout the
reaction

Although the true rate law might be v = k[A][B], we can approximate [B]by [B]0 , its initial value, and write the
​

equations below, which has the form of a first-order rate law:

v = k′[A] k′ = k[B]0

pseudofirst-order rate law → can be defined as the alteration of the true law

Physical Chemistry 27
 this happens when the second-order of bimolecular reaction is forced to behave like a first-order reaction

the dependence of the rate on the concentration of each of the reactants may be found by isolating them in turn (by
having all the other substances present in large excess), and so constructing a picture of the overall rate law

b. method of initial rates → which is often used in conjunction with the isolation method → the rate is measured at the
beginning of the reaction for several different initial concentrations of reactants

Order of reaction → refers to the power dependence of the rate on the concentration of each reactant. It can be classified as: zero-
order, first-order, and second-order.

Thermal activation and the temperature dependence of the rate coefficient

Thermal activation refers to the energy required to initiate a
chemical reaction. As the temperature increases, the rate of a
reaction generally increases due to the increased kinetic energy
of the molecules.

The source of activation energy is typically heat, with

reactant molecules absorbing thermal energy from their
surroundings.

This thermal energy speeds up the motion of the

reactant molecules, increasing the frequency and force
of their collisions, and also jostles the atoms and bonds
within the individual molecules, making it more likely
that bonds will break. In order for the reaction to take place, some or all of the
chemical bonds in the reactants must be broken so that
Once a reactant molecule absorbs enough energy to
new bonds, those of the products, can form.
reach the transition state, it can proceed through the
remainder of the reaction. To get the bonds into a state that allows them to break, the
molecule must be contorted (deformed, or bent) into an
The activation energy of a particular reaction unstable state called the transition state.
determines the rate at which it will proceed.
The transition state is a high-energy state, and some
The higher the activation energy, the slower the amount of energy – the activation energy – must be added
chemical reaction will be. in order for the molecule to reach it.

Because the transition state is unstable, reactant molecules

don’t stay there long, but quickly proceed to the next step of
the chemical reaction.

Source:
https://uen.pressbooks.pub/introductorychemistry/chapter/activa
energy-and-temperature-dependence/

Temperature dependence of rate coefficient can be described using the Arrhenius equation.

This was formulated based on the simple experimental observation that every chemical process gets faster when the
temperature is increased.

the is expressed as:

k = Ae−Ea /RT
​

where k is the rate constant, A is the Arrhenius pre-exponential factor, Ea is the activation energy, R is the gas constant,
and T is the temperature in Kelvin.

The Arrhenius equation shows that the rate of a reaction increases as temperature increases, and that the activation energy
represents the minimum energy required for the reaction to occur.

Physical Chemistry 28
 Source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/The_Live_Textbook_of_Physical_C

The information content of the activation energy and the pre-exponential factor
Activation energy (Ea )→ is the energy level that the reactant molecules must overcome before a reaction can occur.
​

minimum amount of energy required for a chemical reaction

J
it has units of energy per mole of substance, mol in SI.
​

can be thought of as the magnitude of a potential barrier that the reacting molecules need to overcome to initiate a reaction
and convert into products

the primary source of activation energy is thermal energy

endothermic and exothermic reactions:

How to determine the activation energy?

Physical Chemistry 29
 Source: https://www.chem.tamu.edu/rgroup/hughbanks/courses/102/slides/slides17_2.pdf

Pre-exponential factor (A)→ is a constant that can be derived experimentally or numerically. It is also called the frequency factor
and describes how often two molecules collide. To first approximation, the pre-exponential factor is considered constant.

when dealing with the collision theory, the pre-exponential factor is defined as Z and can be derived by considering the
factors that affect the frequency of collision for a given molecule.

the pre-exponential factor is now defined within the collision theory as the following:

8kb T
d2AB
​

​ ​ ​

Note:

Both of these terms are independent of temperature, and they represent experimental quantities that are unique to each
individual reaction.

Since there is no known exception to the fact that a temperature increase speeds up chemical reactions, both A and Ea
are always positive.

In theory, both A and Ea show a weak temperature dependence. However, they can be considered constants at most
experimental conditions, since kinetic studies are usually performed in a small temperature range.︎

7. Reaction mechanisms: Elementary steps. Simplifying methods: steady‐state and pre- equilibrium approximations. The
Lindemann–Hinshelwood mechanism of unimolecular processes. Catalysis and its significance.The kinetics of heterogeneous

Physical Chemistry 30
 reactions, adsorption isotherms (BET, Langmuir). The kinetics of enzyme-catalyzed processes. Non-thermal activation.

ELEMENTARY STEPS
Mechanism for a reaction → is a collection of elementary processes (also called elementary steps or elementary reactions) that
explains how the overall reaction proceeds.

it is a proposal from which you can work out a rate law that agrees with the observed rate laws

Elementary process → also called elementary step or elementary reaction. It is a single step reaction with a single transition state
and no intermediates.

it cannot be broken down into simpler reactions

it expresses how the molecules or ions actually react with each other

the equation in an elementary step represents the reaction at the molecular level, not the overall reaction

Molecularity → is the number of particles involved in an elementary step. Based on numbers of molecules involved in the
elementary step, there are three kinds of elementary steps:

a. Unimolecular step → always follows a first order rate kinetics and occurs when a molecule or ion decomposes by itself

b. Bimolecular step → follows a second order rate kinetics and involves the interaction of tho molecules to form one or more
products

c. Trimolecular step → involves the collision of three molecules

These types are summarized below. In the table, A, B, and C represent reactants, intermediates, or products in the elementary
process.

Note: In a mechanism, elementary steps proceed at various speeds. The slowest step is the rate-determining step. The order
for that elementary process is the order of a reaction, but the concentrations of reactants in that step must be expressed in
terms of the concentrations of the reactants.

Physical Chemistry 31
 Source: https://chem.libretexts.org/Courses/Johns_Hopkins_University/030.356_Advanced_Inorganic_Laboratory/03%3A_Lab_EF-
_Chemical_Kinetics/3.03%3A_Elementary_Steps

Simplifying methods: steady‐state and pre- equilibrium approximations

Steady-state approximation → also known as the quasi-
steady-state approximation, QSSA, assumes that: the
concentration of all reaction intermediates remain constant
and small throughout the reaction.

is a way to simplify the derivation of the rate equation

based on the assumption that one intermediate in the

mechanism will be produced as fast as it is consumed
(i.e. it is at a steady state)

in a multi-step reaction, there will be species that are

intermediates

From Atkins:

assumes that, after an initial induction period, an

interval during which the concentrations of
intermediates, I, rise from zero, and during the
major part of the reaction, the rates of change, of
concentrations of all reaction intermediates are
negligibly small
intermediate → is a species that isn’t one of the initial
this approximation greatly simplifies the discussion reactants or final product(s)
of reaction schemes
produced during the mechanism and will be completely
consumed by the end

assumes that at some point this intermediate will not

have a change in concentration

we can illustrate this steady state using the equation:

d[I]
=0
​

dt
Fig. Example of when an intermediate can be where the concentration of the intermediate is [I]
approximated as a steady-state

Source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_an
State_Approximation

Pre-equilibrium → is a state in which an intermediate is in equilibrium with the reactants and which arises when the rates of
formation of the intermediate and its decay back into
reactants are much faster than its rate of formation of products

Pre-equilibrium Approximations → assumes that the reactants and intermediates of a multi-step reaction exist in dynamic
equilibrium.

like the steady state approximation, it derives an expression for the rate of product formation with approximated
concentrations.

unlike the steady-state method, the pre-equilbrium approximation does so by assuming that the reactants and intermediate
are in equilibrium

Physical Chemistry 32
 Steady-state and pre-equilibrium approximations

both methods are used to solve for a rate of reaction,

but under different conditions

the steady-state method can only be used if the first

step of a reaction is much slower than the second step,
whereas the pre-equilibrium approximation requires the
first step to be faster

these conditions prevent the two methods from

being interchangeable

both the steady state approximation and pre-equilibrium

approximation apply to intermediate-forming
consecutive reactions, in which the product of the first
step of the reaction serves as the reactant for the
second step.

Source:
https://chem.libretexts.org/Bookshelves/Physical_and_Theoretical_Chemistry_Textbook_Maps/Supplemental_Modules_(Physical_an
equilibrium_Approximation?readerView

THE LINDEMANN-HINSHELWOOD MECHANISM OF UNIMOLECULAR PROCESSES

Physical Chemistry 33
 NOTE: 'Unimolecular reactions' usually refer to
first-order gas phase reactions. This is because
these reactions involve a unimolecular step in
which the reactant molecule changes to product.
However, it should be noted that the overall
mechanism involves bimolecular as well as
unimolecular steps.

The first successful explanation of unimolecular

reactions was provided by Frederick Lindemann in
1921 and then elaborated by Cyril Hinshelwood,
hence now known as the Lindemann-
Hinshelwood mechanism (illustrated in Fig.
22.21)

The Lindemann-Hinshelwood mechanism →

breaks down a stepwise reaction into two or more
elementary steps, then it gives a rate constant for
each elementary step.

General Mechanism:

1. According to the Lindemann-Hinshelwood mechanism, a reactant molecule A becomes energetically excited by collision with
another A molecule:

2. The energized molecule A∗ might lose its excess energy either by:

a. Collision with another A molecule (forming no products):

b. Shaking itself apart and forming the products P. That is, it might undergo the unimolecular decay:

Physical Chemistry 34
 Further reading:
https://staff.um.edu.mt/jgri1/teaching/che2372/notes/09/02/unimolecular.html
https://gauravtiwari.org/the-lindemann-theory-of-unimolecular-
reactions/

CATALYSIS AND ITS SIGNIFICANCE

Catalysts provide a means of reducing Ea and increasing the reaction rate.
​

defined as substances that participate in a chemical reaction but are not changed or consumed

they provide a new mechanism for a reaction to occur which has a lower activation energy than that of the reaction without
the catalyst

a catalyst does not appear in the overall stoichiometry of the reaction it catalyzes, but it must appear in at least one of the
elementary reactions in the mechanism for the catalyzed reaction

the catalyzed pathway has a lower Ea, but the net change in energy that results from the reaction (the difference between
the energy of the reactants and the energy of the products) is not affected by the presence of a catalyst

because its lower Ea , the reaction rate of a catalyzed reaction is faster than the reaction rate of the uncatalyzed reaction at
​

the same temperature

because a catalyst decreases the height of the energy barrier, its presence increases the reaction rates of both the forward
and the reverse reactions by the same amount

Physical Chemistry 35
 Three major classes of catalysts:

a. Heterogeneous catalyst

the catalyst is in a different phase from the reactants

at least one of the reactants interacts with the solid surface in a physical process called adsorption in such a way that a
chemical bond in the reactant becomes weak and then breaks

poisons are substances that bond irreversibly to catalysts, preventing reactants from adsorbing and thus reducing or
destroying the catalyst’s efficiency

example: interaction of hydrogen gas with the surface of a metal, such as Ni, Pd, or Pt

Hydrogenation of Ethylene on a Heterogeneous Catalyst

b. Homogeneous Catalysis

the catalyst is in the same phase as the reactant(s)

the number of collisions between reactants and catalyst is at maximum because the catalyst is uniformly dispersed
throughout the reaction mixture

many homogeneous catalysts in industry are transition metal compounds, but recovering these expensive catalysts from
solution has been a major challenge

example: high0density polyethylene and polypropylene are produced by homogeneous catalysis

c. Enzymes

Physical Chemistry 36
 catalysts that occur naturally in living organisms → are almost all protein molecules with typical molecular masses of
20,000-100,000 amu

some are homogeneous catalysts that react in aqueous solution within a cellar compartment of an organism

others are heterogeneous catalysts embedded within the membranes that separate cells and cellular compartments from
their surroundings

substrate → the reactant in an enzyme-catalyzed reaction

because enzymes can increase reaction rates by enormous factors (up to 1017 times the uncatalyzed rate) and tend to
be very specific → typically producing only a single product in quantitative yield

enzymes are usually expensive to obtain, they often cease functioning at temperatures greater than 37 °C, have limited
stability in solution, and have such high specificity that they are confined to turning one particular set of reactants into
one particular product

limited industrial applications: used as ingredients in laundry detergents, contact lens cleaners, and meat tenderizers

enzyme inhibitors → cause a decrease in the reaction rate of an enzyme-catalyzed reaction by binding to a specific
portion of an enzyme and thus slowing or preventing a reaction from occurring

Source: https://chem.libretexts.org/Bookshelves/General_Chemistry/Map%3A_Chemistry_-
_The_Central_Science_(Brown_et_al.)/14%3A_Chemical_Kinetics/14.07%3A_Catalysis

Significance of Catalysis:

Increased reaction rates: Catalysis allows reactions to proceed at a faster rate, making them more efficient and economical.

Lower reaction temperatures: Catalysts can lower the temperature required for a reaction to occur, reducing the energy input
and costs associated with heating.

Enhanced selectivity: Catalysts can selectively promote specific reactions while leaving others unaffected, allowing for the
production of desired products and minimizing unwanted byproducts.

Reduced environmental impact: By increasing reaction rates and selectivity, catalysis can reduce waste production and the
use of hazardous reagents, making processes more environmentally friendly.

Industrial applications: Catalysis plays a crucial role in various industries, such as petroleum refining, chemical production,
pharmaceuticals, and environmental remediation.

Biological catalysis: Enzymes are nature's catalysts and are essential for numerous biological processes, including
metabolism and DNA replication.

Overall, catalysis is of significant importance in both industrial and biological contexts, enabling the efficient and sustainable
production of various materials and compounds.
Source: https://www.britannica.com/science/catalysis

KINETICS OF HETEROGENEOUS REACTIONS, ADSORPTION ISOTHERMS (BET, LANGMUIR)

KINETICS OF HETEROGENEOUS REACTIONS

Heterogeneous reactions refer to reactions that occur between reactants in different phases, such as a gas reacting with a solid
catalyst. The kinetics of heterogeneous reactions involve studying the rate at which these reactions occur.
In heterogeneous reactions, the reactants must come into contact with each other at the interface between the phases. The rate of
the reaction is often determined by the rate at which reactant molecules or ions adsorb onto the catalyst surface, react, and then
desorb as products.

Physical Chemistry 37
Physical Chemistry 38
 FURTHER READING: https://www.chemistry.tcd.ie/assets/pdf/SF Chemical Kinetics Michaelmas 2016_L4-5.pdf
Adsorption Isotherm → is the relationship between the pressure and adsorption amount at a constant temperature

Types of Adsorption isotherms

a. Type I

depicts a monolayer adsorption

the graph can be easily explained using Langmuir Adsorption Isotherm

one adsorption site

ex. ammonia on charcoal at 273 K

b. Type II

shows a large deviation from Langmuir model of adsorption

the intermediate flat region in the isotherm corresponds to monolayer formation

more than one adsorption site

ex. nitrogen on silica gel at 77 K

c. Type III

also shows a large deviation from Langmuir model

explains the formation of multilayer

there is no flattish portion in the curve which indicates that monolayer formation is missing

Physical Chemistry 39
 strong interactions leading to condensation

ex. bromine on silica gel at 352 K

d. Type IV

at lower pressure region of the graph is quite similar to type II

this explains the formation of monolayer followed by multilayer

multiple phase transitions occur due to a mixture of attractive and repulsive interactions

ex. benzene on iron (III) oxide gel at 320 K

e. Type V

explanation is similar to type IV, and both shows phenomenon of capillary condensation of gas

another case for attractive interactions

ex. water vapour on charcoal at 373 K

Source: https://vlab.amrita.edu/?brch=190&cnt=1&sim=606&sub=2

LANGMUIR ADSORPTION ISOTHERM

was developed by Langmuir Irving in 1916 to describe the dependence of the surface coverage of an adsorbed gas on the
pressure of the gas above the surface at a fixed temperature

whilst one of the simplest, it still provides a useful insight into the pressure dependence of the extent of surface adsorption
(extent of adsorption is usually given by fractional coverage, θ)

this method explains adsorption by assuming an adsorbate behaves as an ideal gas at isothermal conditions

Physical Chemistry 40
 according to this model, adsorption and desorption are reversible

it is based on THREE ASSUMPTIONS:

Adsorption cannot proceed beyond monolayer coverage.

All sites are equivalent and the surface is uniform (that is, the surface is perfectly flat on a microscopic scale).

The ability of a molecule to adsorb at a given site is independent of the occupation of neighboring sites (that is, there are no
interactions between adsorbed molecules).

Typical Langmuir Isotherms

Associative → (or non-dissociative) adsorption is when a molecule adsorbs without fragmentation

Dissociative adsorption → when fragmentation occurs during the adsorption process

Physical Chemistry 41
 Source: https://www.slideshare.net/Radhyesham/surfaces1ppt

BET ISOTHERM

explains or describes multilayer molecular adsorption

according to the theory, adsorption takes place only on specific areas of the sample surface (one per molecule) , and doesn’t
stop at monolayer formation but first adsorbed gas molecules provide an adsorption site for subsequent gas molecules
leading to the multilayer adsorption. i.e. after the monolayer has formed, the adsorption process proceeds to the formation of
the multilayer forming second, third, and so forth layers

BET theory also considers that adsorption sites on the solid surface are homogeneous and that adsorption at one site has
no effect on adsorption at nearby sites.

Langmuir and Freundlich adsorption isotherm which fails to explain other isotherms except type I is well explained by the
BET equation

THE BET EQUATION

Physical Chemistry 42
 Cs ⇒ saturation (solubility limit) concentration of the solute (mg/liter)
​

KB ⇒ parameter related to the binding intensity for all layers

​

Note: when Ce << Cs and KB >> 1and K = KB /Cs ⇒ BET isotherm approaches Langmuir isotherm
​ ​ ​ ​ ​

qe ⇒ mass of the material adsorbed (at equilibrium) per mass of adsorbent

​

Ce ⇒ equilibrium concentration in solution when amount adsorbed equals qe 

​ ​

qe /Ce relationships depend on the type of adsorption that occurs, multi-layer chemical, physical adsorption, etc.
​ ​

KINETICS OF ENZYME-CATALYZED PROCESSES

Enzyme-catalyzed processes follow a specific kinetic behavior that differs from uncatalyzed reactions. The kinetics of enzyme-
catalyzed processes can be described using various models, including the Michaelis-Menten equation, Lineweaver-Burk plot,
and the steady-state approximation.

Michaelis-Menten mechanism is a mechanism that describes the behavior of many enzymes. It is a two-step reaction:

1. enzyme binds substrate, creating a Michaelis complex (ES). This step is readily reversible.

2. the substrate is converted to a product and is released from the enzyme. Frequently this step may be considered irreversible
because the concentrations, [E] and [P], are quite small

because [E] is so small and k2 is usually large → the Michaelis complex (ES) is generally present at low concentration
​

treating ES as a steady-state intermediate → we can derive an expression for the reaction rate

at this point it is convenient to also replace [E], because it is often difficult to measure accurately. This is done by expressing the
total enzyme concentration [E]0 as a sum of free enzyme [E] and enzyme and enzyme bound to substrate [ES]
​

although [ES] is small, the approximation [E] ≈ [E]0 is not valid , because [E]0 is usually very small. Substituting for [E], one
​ ​

obtains:

Physical Chemistry 43
 this expression is traditionally written

The Michaelis-Menten equation is widely used to describe the initial rate of an enzyme-catalyzed reaction, where:

v ⇒ reaction velocity
k2 has been replaced by kcat 
​ ​

k−1 +k2
k1
has been replaced by
​

​
​

​ Km 
​ ⇒ the Michaelis constant
Michaelis constant is the substrate concentration at which the reaction velocity (v)is half of its maximum velocity
( Vmax
2 )
​

denoted as Km or sometimes Ks 

​ ​

it indicates how efficiently an enzyme selects its substrate and converts to product

LINEARIZATION METHODS IN THE MICHAELIS-MENTEN MECHANISM

1. One typically measure the initial value of v(rate of appearance of P) at a series of initial values of [S]

2. A second useful plot for enzyme kinetics is called the Lineweaver-Burk plot, which is linear in 1/[S].

it is a graphical representation of the Michaelis-Menten equation

it plots the reciprocal of the reaction rate (1/v) against the reciprocal of the substrate concentration (1/[S])

Physical Chemistry 44
 The steady-state approximation is often used to simplify the analysis of enzyme-catalyzed reactions. It assumes that the
concentration of the enzyme-substrate complex ([ES]) remains constant during the reaction. This approximation allows for the
derivation of rate equations based on the reaction mechanism.
The study of enzyme kinetics is crucial for understanding the behavior and regulation of biochemical reactions in living organisms. It
provides insights into factors that affect enzyme activity, such as temperature, pH, and enzyme inhibitors. Furthermore, enzyme
kinetics plays a vital role in drug discovery, as it helps in the development of enzyme inhibitors for therapeutic purposes.

Source: https://www.ncbi.nlm.nih.gov/books/NBK9924/

Further reading: https://www.news-medical.net/life-sciences/Enzyme-Kinetics.aspx

http://aris.gusc.lv/ChemFiles/MedBiochem2edBaynes07/HTML/bookcontent.cfm@id=hc005010.htm

NON-THERMAL ACTIVATION
Non-thermal activation → refers to the initiation or acceleration of a process without the input of heat energy.

in certain cases, external factors other than temperature can induce or enhance reactions or processes. These factors may
include mechanical agitation, electromagnetic radiation, electrical fields, or chemical stimulation.

EXAMPLES:

Electrochemical reactions → involve the transfer of electrons between substances, typically in an electrolyte solution.
These reactions can occur at room temperature and are used in batteries, fuel cells, and corrosion processes.

Photochemical reactions → are initiated by the absorption of photons (light) by molecules. When a molecule absorbs light
energy, it can undergo various chemical transformations without a substantial increase in temperature.

Physical Chemistry 45
 Photosynthesis in plants and photodegradation of pollutants in the environment are examples of photochemical
processes.

Radiation-induced processes → Ionizing radiation, such as X-rays and gamma rays, can induce chemical changes in
materials without significantly increasing their temperature. This is utilized in various applications, including medical imaging
and sterilization.

Ultrasound and Mechanical activation → High-intensity ultrasound and mechanical forces can induce chemical reactions
or physical changes in materials without the need for elevated temperatures. These techniques are used in sonochemistry
and mechanochemistry, respectively.

Microwave-assisted reactions → Although microwaves can heat materials, they can also selectively heat specific
components in a mixture, promoting chemical reactions at lower overall temperatures compared to conventional heating
methods.

Further reading: https://oszk.ttk.pte.hu/eloadas/PhysChem18.pdf

8. Fundamentals of radiochemistry: The structure and stability of the atomic nucleus. Radioactivity, nuclear reactions.Current
forms of nuclear power, its economic and environmental impact.

THE STRUCTURE AND STABILITY OF THE ATOMIC NUCLEUS

STRUCTURE OF THE ATOMIC NUCLEUS

Nucleus → is a positively charged region at the center of the

atom

It consists of two types of subatomic particles packed

tightly together.

The particles are protons, which have a positive electric

charge, and neutrons, which are neutral in electric
charge.

Outside of the nucleus, an atom is mostly empty space,

with orbiting negative particles called electrons whizzing
through it.

The nucleus of the atom is extremely small. Its radius is

only about 1/100,000 of the total radius of the atom.

If an atom were the size of a football stadium, the

nucleus would be about the size of a pea!
Electrons have virtually no mass, but protons and neutrons
have a lot of mass for their size. As a result, the nucleus
has virtually all the mass of an atom.

Given its great mass and tiny size, the nucleus is very
dense. If an object the size of a penny had the same
density as the nucleus of an atom, its mass would be
greater than 30 million tons!

Source:
https://chem.libretexts.org/Bookshelves/Introductory_Chemistry/Chemistry_for_Changing_Times_(Hill_and_McCreary)/03%3A_Atom
Key Concepts

Atomic number (Z) → of an element is the number of protons in the nucleus of each atom of that element. This means that
the number of protons is the characteristic which makes each element unique compared to all other elements. Elements are
different because of their atomic number.

Physical Chemistry 46
 Mass number (A) → of an atom is the total number of protons and neutrons in its nucleus.
The mass of the atom is a unit called the atomic mass unit (amu). One atomic mass unit is the mass of a proton, or about
1.67 × 10−27 kilograms, which is an extremely small mass.
Isotope → Two or more forms (or atomic configurations) of a given element that have identical atomic numbers (the same
number of protons in their nuclei) and the same or very similar chemical properties but different atomic masses (different
numbers of neutrons in their nuclei) and distinct physical properties.

Thus, carbon-12, carbon-13, and carbon-14 are isotopes of the element carbon, and the numbers denote the
approximate atomic masses.

Among their distinct physical properties, some isotopes (known as radioisotopes) are radioactive because their nuclei
emit radiation as they strive toward a more stable nuclear configuration. For example, carbon-12 and carbon-13 are
stable, but carbon-14 is unstable and radioactive.

STABILITY OF ATOMIC NUCLEUS

The balance of protons and neutrons in a nucleus determines whether a nucleus will be stable or unstable (radioactive). Too many
neutrons or protons can upset this balance making the nucleus unstable.

Key concepts:

Band (Belt) of Stability → represents the area where stable, non-radioactive isotopes exist based on their ratio of neutrons
to protons.

Stable nuclides, if plotted on a graph of number of protons vs. number of neutrons, would all fall in an area enclosed by
two curved lines known as the band of stability.

this area also includes radionuclides because a smooth line cannot be drawn to exclude them

the band of stability stops at element 83 because there are no known stable isotopes above it

in the band of stability, as the number of proton increases, the ratio of protons to neutrons increases

because more neutrons are needed to compensate for the increasing proton-proton repulsion

isotopes occurring above and to the left of the band tend to be beta emitters → they want to lose a neutron and gain a
proton

those lying below and to the right of the band tend to be positron emitters → they want to lose a proton and gain a
neutron

isotopes above element 83 tend to be alpha emitters → they have too many nucleons

stable nuclei with atomic numbers up to about 20 have a neutron : proton ratio of about 1:1

Physical Chemistry 47
 in the odd-even rule → when the number of neutrons
and protons in the nucleus are both even numbers, the
isotope tends to be far more stable than when they are
both odd

out of all the 264 stable isotopes, only 5 have both

odd numbers of both, whereas 157 have even
numbers of both, and the rest have a mixed number

this has to do with the spins of nucleons (both

protons or neutrons spin)

when two protons or neutrons have paired spins (opposite

spins) → their combined energy is less than when they
are unpaired

magic numbers → another rule of nuclear stability is that

isotopes with certain numbers of protons or neutrons tend
to be more stable than the rest

when a nucleus has a number of protons and

neutrons that are the same magic number, it is very
stable

e.g., 42 He, 16
​ ​
40
​
208
8 O 20 C a, 82 P b
​

IMPORTANT NOTES:

Condition of Stability → nuclei stability is achieved when the proton : neutron ratio is optimal

Physical Chemistry 48
 light elements → 1:1 ratio (e.g., 4 He, 12 C, 14 N, 16 O 

elements with medium atomic number → 1:1.4

heavy elements → 1.4:1

any nuclei not fulfilling the optimal ratio are radioactive

the deviation from the optimal ratio predicts the type of radioactive decay:

too many neutrons → negative beta decay

too many protons → positive beta decay; electron capture

heaviest elements → alpha decay; spontaneous fission

groups of nuclei:

isotope → same number of protons

isobar → same number of nucleons

isoton → same number of neutrons

Source: http://www.kentchemistry.com/links/Nuclear/BandStability.htm

RADIOACTIVITY, NUCLEAR REACTIONS

RADIOACTIVITY

Radioactivity → refers to the spontaneous emission of radiation from the nucleus of an atom. It occurs when the nucleus is
unstable and undergoes a process called radioactive decay. During radioactive decay, the nucleus releases particles and/or
electromagnetic radiation, resulting in the transformation of the original nucleus into a different nucleus.
Types of radioactivity:

a. Alpha decay → in this decay, a positively charged particle, identical to the nucleus of Helium 4, emitted spontaneously

this particle consists of two protons and two neutrons

discovered by Ernest Rutherford

characteristic for heavy nuclei (great atomic and mass number)

only common at mass numbers greater than 210 (A>210), except for Samarium (Sm) and Neodymium (Nd)

alpha particles consisting of two protons and two neutrons are very stable because of the filled energy levels both for
protons and neutrons

penetration power:

large mass → highest ionizing power; greatest ability to damage tissues

lower penetration power

collide with molecules very quickly when striking matter; add to electrons → become a harmless helium atom

can be stopped by a piece of paper, clothing, or skin

interaction with matter

interact primarily with matter through Coulomb forces

Physical Chemistry 49
 Applications of alpha radiation:

smoke detectors → radioactive americium releases alpha radiation, which ionizes the air inside the detector.

radioisotopic thermoelectrics → systems using radioactive sources with long half-lives to produce electrical energy

alpha therapy to inhibit tumor growth

Geiger-Nuttall’s Rule → describe the empirical relation between the half-life of alpha decay and the energy of the
emitted alpha particles

b. Beta decay → is a nuclear decay process where an unstable nucleus transmutes and ejects particles to become more
stable

takes place when the ratio of protons and neutrons is not optimal

tends to allow the nucleus to approach the optimal proton : neutron ratio

mass number remains the same but atomic number changes

Two types:

Beta minus decay → occurs whenever a nucleus has too many neutrons

a neutron from the nucleus is transformed into a proton and an electron, with the electron being ejected from the
nucleus

anti-neutrino particle is also emitted

atomic number increases

Physical Chemistry 50
 Beta plus decay → comes from a nucleus with too many protons

a proton from the nucleus is transformed into a neutron and a positron (which is simply a “positive version” of the
electron)

tiny particle known as neutrino is released

atomic number decreases

penetrating power:

are much smaller than alpha particles and therefore, have much less ionizing power (less ability to damage tissue)

their small size gives them much greater penetration power

can be stopped by a one-quarter inch thick sheet of aluminum

the greatest danger occurs when the beta emitting source gets inside of you

interaction with matter:

Physical Chemistry 51
 Applications of beta radiation:

PET Scanners → which use radioactive tracers to image blood flow and other metabolic processes

Beta tracers are also used to investigate the amount of fertiliser reaching different parts of plants (e.g., radioactive
phosphorus)

beta particles are used to monitor the thickness of metal foils and paper

Electron capture → occurs when the atom’s inner orbital electron is absorbed within the nucleus followed by
conversion of a proton to a neutron and emission of a neutrino

the atomic number decreases, but the mass number doesn’t change, which is similar to beta plus decay

accompanied by the emission of:

characteristic x-ray

inner Brehmsstrahlung

Auger electrons

gamma photons

c. Gamma decay → what separates this type of decay process from alpha or beta decay is that no charged particles are
ejected from the nucleus when it undergoes this type of decay

a high energy form of electromagnetic radiation - a gamma ray photon - is released

these gamma ray photons have extremely high energies which are highly ionizing

undergoing gamma decay does not change the structure or composition of the atom, instead, it only changes the energy
of the atom since the gamma ray carries no charge nor does it have an associated mass

penetrating power:

have tremendous penetration power and require several inches of dense material (like lead) to shield them

may pass all the way through a human body without striking anything

are considered to have the least ionizing power and the greatest penetration power.

Physical Chemistry 52
 interaction with matter:

Applications of gamma radiation:

gamma rays are used to detect leaks in pipework

gamma radiation sterilization can kill microorganism

gamma knife surgery → procedure where gamma rays are concentrated into beams that can kill cancerous cells

NUCLEAR REACTIONS

Nuclear reactions involve changes in the nucleus of an atom. These reactions can be induced by various means, such as
bombarding the nucleus with particles or exposing it to high-energy radiation. Nuclear reactions can result in the formation of new
isotopes, the release of energy, and the production of radiation.

Two prominent types of nuclear reactions:

1. Fusion Reaction: In a fusion reaction, two or more atomic nuclei combine to form a heavier nucleus.

this process releases a large amount of energy and is the source of energy in the sun and other stars

it also doesn’t produce highly radioactive fission products

atoms of Tritium and Deuterium (isotopes of hydrogen, Hydrogen-3 and Hydrogen-2, respectively) unite under extreme
pressure and temperature to produce a neutron and a helium isotope

2. Fission Reaction: In a fission reaction, a heavy atomic nucleus splits into two or more lighter nuclei, along with the release of
energy

Physical Chemistry 53
 Fission occurs when a neutron strikes a heavy and unstable atom

In the process, a large and stable quantity of energy and new fissions of atoms continue to be triggered on an ongoing
basis, which is known as a chain reaction.

this process is used in nuclear power plants and atomic bombs

Other important nuclear reactions:

1. Radioactive Decay: Radioactive decay is a spontaneous process in which an unstable atomic nucleus emits particles or
radiation in order to become more stable. This includes alpha decay, beta decay, and gamma decay.

2. Neutron Capture: Neutron capture occurs when a nucleus absorbs a neutron, resulting in the formation of a heavier isotope.
This process is used in nuclear reactors to produce isotopes for various purposes.

Physical Chemistry 54
 3. Nuclear Transmutation: Nuclear transmutation involves the conversion of one element into another by changing the number of
protons in the nucleus through nuclear reactions.

4. Spontaneous Fission: Spontaneous fission can occur only in very heavy elements with an atomic mass number greater than
92.

Spontaneous fission occurs as a result of quantum

tunnelling without the atom having to be struck by a
neutron. The results of spontaneous fission are the same
as that for induced fission, with the element splitting into
two lighter nuclei and releasing neutrons in the process.
These neutrons may induce a nuclear fission chain
reaction if there is enough fissile material present.

It is different to the nuclear fission that occurs in a nuclear

reactor which is induced by neutron bombardment of the
fuel.

Radioactive decay and nuclear reactions have numerous applications in various fields, including medicine, energy production, and
scientific research. They play a crucial role in areas such as nuclear power generation, radiopharmaceuticals for medical imaging
and cancer treatment, and the study of fundamental particles and their interactions.

Current Forms of Nuclear Power

Nuclear power is currently generated through two main methods: nuclear fission and nuclear fusion.

1. Nuclear Fission:
Nuclear fission is the process in which the nucleus of an atom is split into two smaller nuclei, releasing a large amount of energy.
This process is used in commercial nuclear power plants to generate electricity. In nuclear fission, uranium-235 or plutonium-239 is
typically used as fuel. When these fuel rods are placed in a reactor core, they undergo a controlled chain reaction, producing heat.
This heat is then used to generate steam, which drives turbines to produce electricity.

While nuclear fission has the advantage of generating large amounts of energy, it also produces radioactive waste that needs to be
properly managed and stored. The disposal of nuclear waste remains a significant challenge in the nuclear power industry.

MAIN TYPES OF NUCLEAR POWER REACTORS

Physical Chemistry 55
 Pressurized Water Reactor (PWR)

use ordinary water as both coolant and moderator

the design is distinguished by having a primary cooling

circuit which flows through the core of the reactor under
very high pressure, and a secondary circuit in which steam
is generated to drive the turbine

Boiling water reactor (BWR)

has many similarities to the PWR, except that there is only

a single circuit in which the water is at lower temperature
(about 75 times atm) so that it boils in the core to about
285 °C

the reactor is designed to operate with 12-15% of the

water in the top part of the core as steam, and hence with
less moderating effect and efficiency

Pressurized heavy water reactor (PHWR)

has been developed since the 1950s in Canada as the

CANDU, and from 1980s also in India

generally use natural uranium (0.7% U-235) oxide as fuel,

hence needs a more efficient moderator, in this case
heavy water (D2 O ) ​

with the CANDU system, the moderator is enriched (i.e.

water) rather than the fuel – a cost trade-off

The PHWR produces more energy per kilogram of mined

uranium than other designs, but also produces a much
larger amount of used fuel per unit output.

Advanced gas-cooled reactor (AGR)

These are the second generation of British gas-cooled

reactors, using graphite moderator and carbon dioxide as
primary coolant.

The fuel is uranium oxide pellets, enriched to 2.5 - 3.5%, in

stainless steel tubes.

The carbon dioxide circulates through the core, reaching

650°C and then past steam generator tubes outside it, but
still inside the concrete and steel pressure vessel (hence
'integral' design).

Light water graphite-moderated reactor (LWGR)

The main LWGR design is the RBMK, a Soviet design,

developed from plutonium production reactors.

It employs long (7 metre) vertical pressure tubes running Newer PHWR designs such as the Advanced Candu
through graphite moderator, and is cooled by water, which Reactor (ACR) have light water cooling and slightly-
is allowed to boil in the core at 290°C and at about 6.9 enriched fuel.
MPa, much as in a BWR.

Fuel is low-enriched uranium oxide made up into fuel

assemblies 3.5 metres long.

Physical Chemistry 56
 Fast neutron reactor (FNR)

Some reactors do not have a moderator and utilise fast

neutrons, generating power from plutonium while making
more of it from the U-238 isotope in or around the fuel.

They offer the prospect of vastly more efficient use of

uranium resources and the ability to burn actinides which
are otherwise the long-lived component of high-level
nuclear waste.

ADVANCED REACTORS:

Generation I

were developed in the 1950-60s and the last one (Wylfa 1

in the UK) shut down at the end of 2015.

They mostly used natural uranium fuel and used graphite The AGR was developed from the Magnox reactor.
as moderator. Magnox reactors were also graphite moderated and

Generation II CO2 cooled, used natural uranium fuel in metal form,

and water as secondary coolant.
typified by the present US fleet and most in operation
elsewhere.

They typically use enriched uranium fuel and are mostly

cooled and moderated by water.

Generation III

are the advanced reactors evolved from these, the first few
of which are in operation in Japan, China, Russia and the
UAE.

Some are evolutionary from the PWR, BWR and CANDU

designs above, some are more radical departures.

The best-known radical new design has the fuel as large

'pebbles' and uses helium as coolant, at very high
temperature, possibly to drive a turbine directly. With moderation largely due to the fixed graphite,
excess boiling simply reduces the cooling and
Note:
neutron absorbtion without inhibiting the fission
Considering the closed fuel cycle, Generation I-III reactors reaction, and a positive feedback problem can arise.
recycle plutonium (and possibly uranium), while
Generation IV are expected to have full actinide recycle.

Small Modular Reactors (SMRs) → are advanced nuclear

reactors that have a power capacity of up to 300 MW(e) per unit,
which is about one-third of the generating capacity of traditional
nuclear power reactors

Small – physically a fraction of the size of a conventional

nuclear power reactor.

Modular – making it possible for systems and components to

be factory-assembled and transported as a unit to a location Generation IV
for installation.
Gas-cooled fast reactor (GFR) → will be high
Reactors – harnessing nuclear fission to generate heat to temperature units - typically 800-850 °C
produce energy.
Lead-cooled fast reactor (LFR) → is a flexible
Floating Nuclear Power Plant fast neutron reactor which can use depleted

Physical Chemistry 57
 Rosatom in Russia has set up a subsidiary to supply floating uranium or thorium fuel matrices, and burn
nuclear power plants ranging in size from 70 to 600 MWe. actinides from LWR fuel

These will be mounted in pairs on a large barge, which will be Molten salt reactor (MSR) → two variants: one a
permanently moored where it is needed to supply power and fast reactor with fissile material dissolved in the
possibly some desalination to a shore settlement or industrial circulation fuel salt; the other with solid particle
complex. fuel in graphite and the salt functioning only as
coolant.
The first has two 40 MWe reactors based on those in
icebreakers and operates at a remote site in Siberia. Sodium-cooled fast reactor (SFR) → uses liquid
sodium as the reactor coolant, allowing high
power density with low coolant volume, at low
pressure

Supercritical water-cooled reactor (SCWR) →

is a very high-pressure water-cooled reactor
which operates above the thermodynamic critical
point of water (374ºC, 22 MPa) to give a thermal
efficiency about one-third higher than today's light
water reactors from which the design evolves

Very high-temperature gas reactor (VHTR) →

are graphite-moderated, helium-cooled reactors

Given their smaller footprint, SMRs can be sited

on locations not suitable for larger nuclear power
plants.

proposed SMR designs are generally simpler, and

the safety concept for SMRs often relies more on
passive systems and inherent safety
characteristics of the reactor, such as low power
and operating pressure

2. Nuclear Fusion:
Nuclear fusion is the process in which two light atomic nuclei combine to form a heavier nucleus, releasing a tremendous amount
of energy. This process is the fundamental source of energy in stars, including the sun. However, achieving controlled nuclear fusion
on Earth is still a significant scientific and engineering challenge.

Physical Chemistry 58
 Nuclear fusion has the potential to provide a virtually limitless and clean source of energy, as it uses isotopes of hydrogen, such as
deuterium and tritium, as fuel. Fusion reactors would produce significantly less radioactive waste compared to fission reactors.
Researchers and scientists around the world are actively working on developing practical fusion reactors, but it is still a technology
that is not yet commercially viable.

NUCLEAR FUSION TECHNOLOGIES

Magnetic Confinement Inertial Confinement

in magnetic confinement fusion (MCF), hundreds of cubic in inertial confinement fusion, laser or ion beams are
meters of D-T plasma at a density of less than a milligram focused very precisely onto the surface of the target, which
per cubic meter are confined by a magnetic field at a few is a pellet of D-T fuel, a few mm in diameter
atmosphere pressure and heated to fusion temperature
Japan “Fast ignition” → suggests that ignition may be
the most effective magnetic configuration is toroidal, achieved at lower temperature with a second very intense
shaped like a doughnut, in which the magnetic field is laser pulse guided through a millimetre-high gold cone into
curved around to form a closed loop the compressed fuel, and timed to coincide with the peak
compression.
several types of toroidal confinement system:
UK First Light Fusion → s researching inertial fusion energy
tokamaks → the toroidal field is created by a series of
(IFE) with a focus on power driver technology using an
coils evenly spaced around the torus-shaped reactor,
asymmetric implosion approach.
and the poloidal field is created by a system of
horizontal coils outside the toroidal magnet structure US National Ignition Facility → is a large laser-based
inertial confinement fusion research device at the Lawrence
sterallator → Lyman Spitzer devised and began work
Livermore National Laboratory in California. It focuses 192
on the first fusion device – a stellarator – at the
powerful laser beams into a small target in a few billionths
Princeton Plasma Physics Laboratory in 1951. Because
of a second, delivering more than 2 MJ of ultraviolet energy
stellarators have no toroidal plasma current, plasma
and 500 TW of peak power.
stability is increased compared with tokamaks.
‘Z-pinch’→ uses a strong electrical current in a plasma to
reversed field pinch (RFP) devices → differ from
generate X-rays, which compress a tiny D-T fuel cylinder.
tokamaks mainly in the spatial distribution of the
toroidal magnetic field, which changes sign at the edge
Hybrid fusion
of the plasma.
Fusion can also be combined with fission in what is referred
Magnetized target fusion (MTF) to as hybrid nuclear fusion where the blanket surrounding
the core is a subcritical fission reactor.
also referred to as magneto-inertial fusion (MIF), is a
pulsed approach to fusion that combines the compressional The fusion reaction acts as a source of neutrons for the
heating of inertial confinement fusion with the magnetically surrounding blanket, where these neutrons are captured,
reduced thermal transport and magnetically enhanced resulting in fission reactions taking place.
alpha heating of magnetic confinement fusion.
These fission reactions would also produce more neutrons,
thereby assisting further fission reactions in the blanket.

FUSION RESEARCH

International Thermonuclear Experimental Reactor (ITER) Joint European Torus (JET)

In southern France, 35 nations* are collaborating to build is the largest and most successful fusion experiment in the
the world's largest tokamak, a magnetic fusion device that world and one of the key research facilities of the European
has been designed to prove the feasibility of fusion as a Fusion Programme.
large-scale and carbon-free source of energy based on the
JET serves as the “test-bed” for ITER and is often referred
same principle that powers our Sun and stars.
to as “Little ITER”
The machine has been designed specifically to:
At the core of JET is the vacuum vessel where the fusion
achieve a deuterium-tritium plasma in which the fusion plasma is confined by means of strong magnetic fields and
conditions are sustained mostly by internal fusion plasma currents (up to 4 tesla and 5 mega amperes)
heating
Salient features:

Physical Chemistry 59
 generate 500 MW of fusion power in its plasma flexible and powerful plasma auxiliary heating system,
consisting of Neutral Beam Injection (34 megawatts),
contribute to the demonstration of the integrated
Ion Cyclotron Resonance Heating (10 megawatts) and
operation of technologies for a fusion power plant
Lower Hybrid Current Drive (7 megawatts).
test tritium breeding
An extensive diagnostic suite of around 100 individual
demonstrate the safety characteristics of a fusion instruments capturing up to 18 gigabytes of raw data
device per plasma pulse.

A high frequency pellet injector for plasma refuelling

and for ELM pacing studies.

A massive gas injection valve for plasma disruption

studies.

Capabilities to operate with tritium fuel – unique among

today’s tokamaks

Beryllium handling facilities, allowing use of beryllium

plasma-facing components.

Remote handling facilities that allow advanced

engineering work to be performed inside the vacuum
vessel without the need for manned access.

Korean Superconducting Tokamak Reactor (KSTAR)

a superconducting fusion device also known as the Korean

artificial sun, set the new world record as it succeeded in
maintaining the high temperature plasma for 20 seconds
with an ion temperature over 100 million degrees (Celsius).

FURTHER READING: https://world-nuclear.org/information-

library/current-and-future-generation/nuclear-fusion-power.aspx

Economic and Environmental Impact

Nuclear power has both economic and environmental impacts:

Economic Impact:

Nuclear power plants require substantial initial investments for construction and infrastructure development.

The cost of nuclear fuel, such as uranium, can also contribute to the overall operational costs of nuclear power plants.

However, nuclear power plants have the advantage of producing large amounts of electricity, which can help meet the energy
demands of a growing population.

Environmental Impact:

Nuclear power plants do not produce greenhouse gas emissions during electricity generation, unlike fossil fuel-based power
plants. This makes them a low-carbon energy source.

Physical Chemistry 60
 However, the mining, processing, and transportation of uranium fuel do have environmental impacts.

The management and disposal of nuclear waste also pose environmental challenges, as radioactive materials need to be stored
securely for long periods.

Nuclear accidents, such as the Chernobyl and Fukushima disasters, have highlighted the potential risks associated with nuclear
power.

Overall, nuclear power is a complex topic with both benefits and challenges. It provides a significant source of electricity generation,
but the management of nuclear waste and the potential for accidents remain important considerations in the adoption and expansion
of nuclear power as an energy source.

9. Physical chemistry of colloids: The definition of colloid systems, their classification and stability. Types of interfaces and
adsorption. Fundamentals of nanotechnology.

The definition of colloid systems, their classification and stability.

DEFINITION OF COLLOID SYSTEMS

Colloids or disperse phase → is a dispersion of small particles of one material in another

are complex systems consisting of dispersed particles of one substance, known as the dispersed phase, dispersed throughout
another substance, known as the dispersion medium.

in this context, “small” means something less than 500 nm in diameter (about the wavelength of visible light)

in general, colloidal particles are aggregates of numerous atoms or molecules, but are too small to be seen with an ordinary
optical microscope

they pass through most filter papers, but can be detected by light-scattering and sedimentation

Colloids can exist in various states, including liquid, solid, and gas, and exhibit unique properties due to the interaction between
the dispersed phase and the dispersion medium.

CLASSIFICATION OF COLLOIDAL SYSTEMS

1. Classification Based on Physical State of Dispersed Phase and Dispersion

Medium

Depending upon whether the dispersed phase and the dispersion medium are solids, liquids
or gases, eight types of colloidal systems are possible. A gas mixed with another gas forms a
homogeneous mixture and hence is not a colloidal system.

a. Sol → is a dispersion of a solid in a liquid (i.e., clusters of gold atoms in water) or of a solid in a solid (i.e., ruby glass, which
is a gold-in-glass sol, and achieves its color by light scattering)

b. Aerosol → is a dispersion of a liquid in a gas (like a fog and many sprays) or a solid in a gas (such as smoke); the particles
are often too large enough to be seen with a microscope. Aerosol colloids often exhibit a mist-like appearance.

Physical Chemistry 61
 c. Emulsion → is a dispersion of a liquid in a liquid (such as milk). Emulsion colloids can have a cloudy or creamy
appearance.

d. Gel → colloidal solutions in which minute liquid droplets are dispersed into a solid dispersion medium, it is also called solid
emulsion. It is a semi-rigid mass of a lyophilic sol in which all the dispersion medium has penetrated into the sol particles.
Gel colloids have a semi-solid or jelly-like consistency.

e. Foam → consist of a gas dispersed phase and a liquid dispersion medium. Foam colloids have a light and frothy texture.

2. Classification of Colloids based on Interaction between dispersed phase and dispersion medium

a. Lyophilic → solvent attracting

colloidal particles that are attracted to water molecules. This attraction allows the particles to remain suspended in water
for long periods.

colloidal solutions where the particles of the dispersed phase have a strong affinity for the particles of the dispersion
medium.

examples: gum, starch, gelatin, proteins

b. Lyophobic → solvent repelling

colloidal particles that are not attracted to water molecules. This means that they will quickly settle out of solution if left
undisturbed.

colloidal solutions where the particles of the dispersed phase have a weak affinity for the particles of the dispersion
medium.

examples: many metals, such as gold and silver

Note: If the solvent is water, the terms hydrophilic and hydrophobic, respectively, are used instead.

3. Classification of Colloids based on Properties of Sol Particles

a. Multimolecular colloids → formed when small molecules or atoms combine to form a species that falls within the colloidal
size range.

example: a sulfur solution consisting of thousands of S8 particles.

​

b. Macromolecular colloids → biomolecules such as enzymes or proteins that are larger in size and form colloids when
properly dispersed.

example: rubber, cellulose, starch

c. Associated colloids → are substances whose molecules are amphiphilic, meaning that they contain both a non-polar
hydrophobic part and a polar hydrophilic part.

4. Classification Based on Dispersion Medium

a. Hydrosols → are colloids in which water is the dispersion medium.

b. Alcosols → are colloids in which alcohol is the dispersion medium. Solutions containing ethanol and methanol are
examples of alcosols.

c. Acrosols → are colloids in which air is the dispersed phase.

Further reading: https://www.geeksforgeeks.org/colloids/

https://unacademy.com/content/jee/difference-between/lyophilic-and-lyophobic-colloids/

Stability of colloids

Colloidal systems differ widely with respect to stability. Some of them can be preserved unchanged for long periods of time; others
are comparatively unstable being more sensitive to various influences.

There are two kinds of processes which lead to the disintegration of colloidal systems and which under certain condition can take
place spontaneously. These are: sedimentation processes and coagulation processes.
Key Concepts:

Physical Chemistry 62
 Kinetic and aggregate stability → characterize colloidal systems stability with respect to sedimentation process and the
changing in particle size (coagulation)

Kinetic stability → is determined by two conflicting processes: sedimentation of the particles and their thermal
motion

Aggregate stability → is a measure of the ability of a colloidal system to preserve its degree of dispersion

it is due to the fact that the particles of the dispersed phase are electrically charged and are surrounded by a solvate
(hydrate) shell

Source: http://chemistry.univer.kharkov.ua/files/Module 2. Lecture 9.pdf

colloids are thermodynamically unstable with respect to the bulk, which can be expressed by noting that because the change
in Gibbs energy, dG, when the surface area of the sample changes by dσ at constant temperature and pressure is dG =
γdσ , where γ is the interfacial surface tension, it follows that dG < 0if dσ < 0
the survival of colloids must therefore be a consequence of the kinetics of collapse: colloids are thermodynamically unstable
but kinetically non-labile

Electrical double layer → a major source of kinetic non-lability of colloids is the existence of an electric charge on the
surfaces of the particles. On account of this charge, ions of opposite charge tend to cluster nearby, and an ionic atmosphere
is formed, just as for the ions. We need to distinguish two regions of charge:

first: there is a fairly immobile layer of ions that adhere tightly to the surface of the colloidal particle, and which may
include water molecules (if that is the support medium)

the radius of the sphere that captures this rigid layer is called the radius of shear and is the major factor
determining the mobility of the particles

zeta potential or the electrokinetic potential → the electric potential at the radius of shear relative to its value in
the distant, bulk medium

second: the charged unit attracts an oppositely charged atmosphere of mobile ions

electrical double layer → the inner shell of charge and the outer ionic atmosphere

A double layer around a charged particle formed by the particle surface charge and its counter ions, forming an ionic
cloud surrounding the particle. An electrical double layer is often called an electrical diffuse double layer, since the
distribution of counter ions in the ionic cloud takes a diffusive structure due to thermal motion of ions.

an electric double layer consists of three parts:

Physical Chemistry 63
 surface charge → charged ions (commonly negative) adsorbed on the particle surface

Stern layer → counterions (charged opposite to the surface charge), attracted to the particle surface and closely
attached to it by the electrostatic force

diffuse layer → a film of the dispersion medium (solvent) adjacent to the particle. This layer contains free ions with
a higher concentration of the counterions. The ions of the diffuse layer are affected by the electrostatic force of the
charged particle.

DLVO (Derjaguin-Landau-Verwey-Overbeek) Theory → explains the stability of colloidal suspension

it suggests that the stability of a colloidal system is

determined by the sum of these van der Waals
attraction and electrical double layer repulsive
forces that exist between particles as they approach
each other due to the Brownian motion they are
undergoing

this theory proposes that an energy barrier resulting

from the repulsive forces prevents two particles
approaching one another and adhering together

but if the particles collide with sufficient energy to

overcome that barrier, the attractive force will pull
them into contact where they adhere strongly and
irreversibly together

therefore, if particles have a sufficiently high

repulsion, the dispersion will resist flocculation and
Figure 1: The net energy is given by the sum of the double
the colloidal system will be stable
layer repulsion and the van der Waals attractive forces that
if a repulsion mechanism does not exist then the particles experience as they approach one another
flocculation or coagulation will eventually take place

in certain situations, there is a possibility of a

“secondary minimum” where a much
weaker and potentially reversible adhesion between
particles exists together (figure 2).

Physical Chemistry 64
 These weak flocs are
sufficiently stable not to be broken up by Brownian
motion, but may dissociate under an externally
applied force such
as vigorous agitation.

Figure 2: Schematic diagram of the variation of free energy

with particle separation at higher salt concentrations
showing the possibility of a secondary minimum

How can colloidal stability be achieved?

Source: file:///C:/Users/bosqu/Downloads/Derjaguin-
Landau-Verwey-Overbeek- There are two fundamental mechanisms that affect
Theory%20(DLVO%20theory).pdf dispersion stability:

Steric repulsion → involves polymers added to the

system adsorbing onto the particle surface and
preventing it from coming into close contact

If enough polymer adsorbs, the thickness of the

coating is sufficient to keep particles separated by
steric repulsions between the polymer layers, and
at those separations the van der Waals forces are
too weak to cause the particles to adhere.

Electrostatic or charge stabilization → this is the

effect on particle interaction due to the distribution of
charged
species in the system.

Flocculation → aggregation of the particles arising from

the stabilizing effect of this secondary minimum. The
flocculated material can often be redispersed by agitation
becasue the well is shallow.

Coagulation → the irreversible aggregation of distinct

particles into large particles, occurs when the separation
of the particles is so small that they enter the primary
minimum of the potential energy curve and van der Waals
forces are dominant

Schulze-Hardy rule → also known as the Schulze-Hardy rule of coagulation, states that the stability of a colloidal system is
inversely proportional to the valence of the counter-ions present in the dispersion medium.

Physical Chemistry 65
 the amount of electrolyte required for the coagulation of a definite amount of a colloidal solution is dependent on the
valences of the coagulating ion

multivalent counter-ions → have a greater ability to neutralize the charge on the colloidal particles, leading to a higher
likelihood of coagulation or flocculation.

monovalent counter-ions → have a weaker effect on the stability of the colloidal system. The Schulze-Hardy rule
provides a useful guideline for predicting and controlling the stability of colloidal suspensions.

Source: http://chemistry.univer.kharkov.ua/files/Module 2. Lecture 9.pdf

Types of Interfaces and Adsorption

Interfaces play a crucial role in various physical and chemical processes. They are the boundaries between two different phases,
such as between a solid and a liquid or between two immiscible liquids. Here are some common types of interfaces:

1. Solid-Liquid Interface: This interface occurs between a solid and a liquid phase. Adsorption at this interface can involve
various processes, such as the formation of a solvation layer or the adsorption of ions or molecules onto the solid surface.

2. Liquid-Liquid Interface: This interface occurs between two immiscible liquid phases. Adsorption at this interface can result in
the formation of an interfacial layer or the partitioning of solutes between the two liquids.

3. Gas-Liquid Interface: This interface occurs between a gas and a liquid phase. Adsorption at this interface can involve the
absorption of gas molecules into the liquid or the formation of a gas film on the liquid surface.

4. Gas-Solid Interface: This interface occurs between a gas and a solid phase. Adsorption at this interface can involve the
adsorption of gas molecules onto the solid surface, which can lead to various phenomena such as gas-solid reactions or the
formation of a gas film on the solid surface.

Adsorption is the process of accumulation of molecules or ions at the interface or surface of a material. It can occur through various
mechanisms, including physical adsorption (van der Waals forces) and chemical adsorption (chemical bonding). The adsorption
process is influenced by factors such as temperature, pressure, and the nature of the adsorbent and adsorbate.

Understanding the different types of interfaces and adsorption processes is essential in fields such as surface science, material
science, and catalysis, as it plays a significant role in determining the behavior and properties of materials at the nanoscale.

Source: https://www.britannica.com/science/colloid

FUNDAMENTALS OF NANOTECHNOLOGY
Nanotechnology is a field of science and technology that deals with the manipulation and control of matter at the nanoscale, typically
within the range of 1 to 100 nanometers. It involves the study, design, creation, and application of materials, devices, and systems
with unique properties and functions at the nanoscale.

Fundamentals of Nanotechnology:

1. Size and Scale: Nanotechnology focuses on structures and phenomena at the nanoscale, which is characterized by extremely
small dimensions. At this scale, materials and systems exhibit unique properties and behaviors that differ from their bulk
counterparts.

2. Bottom-Up and Top-Down Approaches: Nanotechnology employs two main approaches for the fabrication and assembly of
nanoscale structures. The bottom-up approach involves building structures from individual atoms or molecules, allowing for
precise control over their properties. The top-down approach involves the miniaturization of larger structures to the nanoscale
through techniques such as lithography and etching.

3. Quantum Effects: At the nanoscale, quantum effects become more prominent, and the laws of classical physics may no longer
apply. Quantum confinement, tunneling, and quantum coherence are examples of quantum phenomena that play a crucial role
in nanoscale systems.

4. Interdisciplinary Nature: Nanotechnology is highly interdisciplinary, drawing knowledge and techniques from various fields
such as physics, chemistry, biology, materials science, and engineering. This multidisciplinary approach allows for the
exploration and development of nanoscale materials and devices with diverse applications.

5. Properties and Applications: Nanomaterials exhibit unique properties due to their small size and high surface-to-volume ratio.
These properties can be tailored by controlling the size, shape, and composition of the nanomaterials. Nanotechnology finds

Physical Chemistry 66
 applications in various fields, including electronics, medicine, energy, environmental remediation, and information technology.

6. Characterization Techniques: Characterizing nanoscale structures and properties requires specialized techniques. Scanning
probe microscopy, transmission electron microscopy, atomic force microscopy, and spectroscopic techniques are commonly
used to visualize and analyze nanomaterials.

7. Ethical and Societal Considerations: As with any emerging technology, nanotechnology raises ethical, environmental, and
societal concerns. These include potential risks to human health, the environment, and privacy, as well as the equitable
distribution of benefits and risks associated with nanotechnology.

Nanotechnology holds great promise for advancements in various fields and has the potential to revolutionize industries and
improve our quality of life. However, it is important to ensure responsible development and use of nanotechnology to address
potential risks and maximize its benefits.

Source: https://www.nano.gov/nanotech-101/what/definition

Further reading: https://ec.europa.eu/programmes/erasmus-plus/project-result-content/fe710461-5da6-42bd-9351-

828558ab56da/Nanotechnology 1 Fundamentals of Nanotechnology.pdf
10. Electrochemistry: Chemical reaction caused by current, electrolysis. Electrode potential and electromotive force. Different
types of electrodes. Electric current production with chemical reactions: the thermodynamics of Galvanic cells and kinetic aspects of
electricity generation.

CHEMICAL REACTION CAUSED BY CURRENT, ELECTROLYSIS

Electrolysis → is a chemical reaction caused by an electric current.

it involves the decomposition of a compound into its

constituent elements or ions using an electric current

the compound being electrolyzed is called the

electrolyte, and it can be either a liquid or a molten
substance

During electrolysis, the positive electrode, called the

anode, attracts the negatively charged ions (anions) in
the electrolyte, causing them to lose electrons and
undergo oxidation. The negative electrode, called the
cathode, attracts the positively charged ions (cations) in
the electrolyte, causing them to gain electrons and
undergo reduction.

Key Concepts:

A Galvanic cell converts chemical energy into electrical energy. An electrolytic cell converts electrical energy into chemical
energy.

Physical Chemistry 67
 Faraday’s Law of Electrolysis → based on the electrochemical research of Michael Faraday, which show the quantitative
relationship between the substance deposited at electrode and the quantity of electric charge or electricity passed

Faraday’s First Law of Electrolysis → states that “The mass of a substance deposited at any electrode is directly
proportional to the amount of charge passed.”

it can be expressed as m ∝ Q; where Q is the electric charge measured in Coulomb

the relationship is: charge(Coulombs) = current(amps) × time(sec)

Q=I×t

Faraday’s Second Law of Electrolysis → states that “in order to produce one mole of a metal, one, two, three, or
another whole number of moles of electrons must be consumed.”

The charge on one mole of electrons is known as Faraday, and given the symbol F. 1 F araday =
96, 500 C/mol 
The charge on a given number of moles of electrons, n(e− ), may be calculated by:

Q = n(e− ) × F
w
It can also be expressed as: − w1
2
​

​
​ = −E
E2
1
; where E is the equivalent weight of the substances
​

​
​

Applications of Electrolysis

Plating a thin film of metal on surfaces of other metals to improve the appearance or prevent corrosion

Extraction of reactive metals such as sodium and aluminum from their ores

Industrial production of sodium hydroxide, copper, chlorine, and hydrogen

Recharging of car batteries and other rechargeable cells, such as lithium batteries

Increasing the thickness of the surface oxide layer on aluminum metal to improve its resistance to corrosion

ELECTRODE POTENTIAL AND ELECTROMOTIVE FORCE

Electrode Potential: Electrode potential, also known as redox potential, is a measure of the tendency of an electrode to undergo
reduction or oxidation. It is defined as the potential difference between an electrode and its surrounding solution when no current is
flowing.

Reference Electrode: Electrode potential is measured with respect to a reference electrode, such as the standard hydrogen
electrode (SHE) or the standard calomel electrode (SCE). The potential of the reference electrode is defined as zero volts.

Electromotive Force (EMF): Electromotive force, often referred to as cell voltage or cell potential, is the potential difference
between two electrodes in an electrochemical cell. It is a measure of the cell's ability to drive an electric current through an external
circuit.

Reference Standard: EMF is measured under standard conditions, which include standard concentrations, temperature,
and pressure. Standard electrode potentials (also known as standard reduction potentials) are used to calculate EMF.

In an electrochemical cell, the electrode potential and the concentrations of the reactants and products determine the cell potential
or EMF. This potential difference is responsible for the flow of electrons from the anode to the cathode in the cell, driving the
chemical reactions.

Physical Chemistry 68
 The electrode potential and electromotive force are important concepts in understanding and analyzing electrochemical reactions
and cells.

DIFFERENT TYPES OF ELECTRODES

Reference Electrode: A reference electrode is used as a
standard to measure the potential of other electrodes.
Common reference electrodes include the Standard
Hydrogen Electrode (SHE), Silver/Silver Chloride electrode
(Ag/AgCl), and Calomel Electrode (Hg/Hg2Cl2).

Glass Electrode: A glass electrode is commonly used in

pH measurements. It consists of a glass membrane that
responds to changes in hydrogen ion concentration.

Ion-Selective Electrode: An ion-selective electrode is

designed to selectively respond to a specific ion in a
solution. Examples include the pH electrode, fluoride ion-
selective electrode, and potassium ion-selective electrode.

Physical Chemistry 69
 Working Electrode: A working electrode is the electrode
where the electrochemical reaction of interest occurs. It can
be made of various materials depending on the specific
application, such as platinum, gold, or carbon.

Counter Electrode: A counter electrode completes the

electrical circuit in an electrochemical cell. It is often made
of an inert material like platinum or graphite.

Indicator Electrode: An indicator electrode is used to

detect and measure the concentration of an analyte in a
solution. Examples include the oxygen electrode and the
nitrate ion-selective electrode.

Auxiliary Electrode: An auxiliary electrode, also known as

a reference electrode, is used in conjunction with a working
electrode to complete an electrochemical cell. It is typically
made of an inert material like platinum or graphite.

Electric current production with chemical reactions: the thermodynamics of Galvanic cells and
kinetic aspects of electricity generation.
The production of electric current through chemical reactions involves the use of Galvanic cells. These cells rely on the principles of
thermodynamics and kinetics to generate electricity.

In a Galvanic cell, the chemical reactions taking place are spontaneous and result in the conversion of chemical energy into
electrical energy. The cell consists of two half-cells, each containing an electrode immersed in an electrolyte solution. These half-
cells are connected by a conductive material, such as a wire or a salt bridge.

The thermodynamics of Galvanic cells are governed by the Gibbs free energy change (ΔG) of the overall reaction. If the
Gibbs free energy change is negative (ΔG < 0), the reaction is spontaneous and can produce electrical energy. The magnitude of
ΔG determines the maximum voltage that can be obtained from the cell.

The kinetics of electricity generation in Galvanic cells involve the rate at which the chemical reactions occur. Factors such
as the concentration of reactants, temperature, and electrode surface area can influence the rate of the reactions. Efficient electrode

Physical Chemistry 70
 materials and catalysts are often used to enhance the kinetics of the reactions and improve the overall performance of the cell.

Overall, the thermodynamics and kinetics of Galvanic cells play crucial roles in the production of electric current through chemical
reactions. Understanding these principles is essential for the design and optimization of electrochemical systems for energy
generation.
Source: https://www.nano.gov/nanotech-101/what/definition

Further reading: http://www.katedrachf.umcs.lublin.pl/cwiczenia/Ang/PhysChem/Cw-3.pdf

https://assets.researchsquare.com/files/rs-115734/v1_covered.pdf?c=1631848049

Physical Chemistry 71