Unit IV
Unit IV
Unit IV
Tech
A system and its surroundings are fundamental concepts used to analyse and describe the exchange of
energy and matter.
System:
A system is a specific portion of the universe that is chosen for analysis or observation.
It can be as simple as a container of gas, a living organism, or as complex as an entire chemical process or
even the entire universe.
Surroundings:
The surroundings, also known as the environment, refer to everything outside the system under
consideration. The surroundings include everything other than the system.
It includes everything that can potentially interact with the system, influencing its behaviour or being
influenced by the system.
The surroundings provide a reference point for understanding the exchanges of energy and matter with the
system.
Universe: System and the surroundings together constitute the universe.
The universe = The system + The surroundings
Boundaries: The boundaries of a system are defined to separate it from its surroundings, allowing for a clear
distinction between what is being studied and what is external to the study.
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Examples of open systems include a boiling pot of water, where both heat and steam can escape, and living
organisms that exchange energy and nutrients with their surroundings.
2. Closed System:
A closed system allows the transfer of energy but not mass across its boundaries.
While the system can exchange heat with its surroundings, the total mass of the system remains constant.
A sealed container with gas or a hot water bottle with closed caped undergoing a temperature change but not
the mass inside the bottle is an example of a closed system.
3. Isolated System:
An isolated system does not exchange energy or matter with its surroundings.
Water kept in a thermos flask is an example of Isolated system.
In summary, the distinction between these systems is based on the ability to exchange energy and matter with
the surroundings. Open systems allow both, closed systems allow only energy exchange, and isolated systems
allow neither energy nor matter exchange with the surroundings.
Diathermic Walls:
Diathermic walls are walls that allow the transfer of heat between the system and its surroundings. In other
words, these walls permit the flow of thermal energy across them.
Example: Consider a container with a diathermic wall separating two chambers. If you heat one side of the
wall, the heat can pass through, and the other side of the wall will also experience a temperature increase. An
everyday example is a metal container with a thin conducting diathermic partition.
Adiabatic Walls:
Adiabatic walls are walls that do not allow the transfer of heat between the system and its surroundings. In
an adiabatic process, there is no heat exchange with the surroundings, meaning the system is thermally
isolated.
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Example: Imagine a perfectly insulated and rigid container with adiabatic walls. If you heat the gas inside this
container, the heat generated or absorbed by the gas will not be transferred to the surroundings. This could be
exemplified by a thick layer of insulating material around the container, preventing heat exchange.
Extensive Properties: An extensive property is a property that depends on the amount of matter (mass) in a
sample.
For example, mass, weight, volume, internal energy, enthalpy, heat capacity, etc. are extensive properties.
Intensive Properties: An intensive property is a property of matter that depends only on the type of matter in
a sample and not on the amount.
For example, Color, temperature, solubility, specific heat, refractive index etc are intensive properties.
Note: The ratio of two extensive properties is an intensive property. Such as, density being the ration of
two extensive properties mass and volume becomes intensive in nature.
• Isothermal Process:
An isothermal process is one in which the temperature of a system remains constant throughout the entire
process.
Characteristics: During an isothermal process, the system exchanges heat with its surroundings in such a way
that the temperature remains constant.
In mathematical terms, for an ideal gas, the process follows the equation
PV = constant
• Adiabatic Process:
An adiabatic process is one in which there is no heat exchange between the system and its surroundings.
Characteristics: In an adiabatic process, the system's internal energy changes without the transfer of heat.
This can happen rapidly, and the relationship between pressure (P), volume (V), and temperature (T) for an
ideal gas follows the equation
γ
PV = constant
• Isobaric Process:
An isobaric process is one in which the pressure of the system remains constant.
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Characteristics: During an isobaric process, the system may exchange heat with its surroundings, and work
may be done on or by the system. In mathematical terms, for an ideal gas, the process follows the equation
𝑽 = Constant
𝑻
• Isochoric Process:
An isochoric process is one in which the volume of the system remains constant.
Characteristics: During an isochoric process, no work is done because there is no change in volume. The heat
exchange may still occur, resulting in a change in temperature. For an ideal gas, the process follows the
equation
𝑷 = Constant
𝑻
The first law of thermodynamics, also known as the law of energy conservation, states that energy cannot
be created or destroyed in an isolated system. In other words, the total energy of an isolated system remains
constant. The first law is often expressed mathematically as:
ΔU = Q − W
where:
ΔU is the change in internal energy of the system,
Q is the heat added to the system, and
W is the work done by the system on its surroundings.
The derivation of the first law involves considering the work done by and on the system, as well as the heat
added to or removed from the system.
Derivation:
Let Q amount of heat is supplied to a system containing one mole of gas in a cylinder filled with weightless,
frictionless movable piston. The gas expands from T1 to T2 at constant pressure
It is found that Q > W
So, it supposed that (Q-W) amount of heat goes to increase internal energy of the system. So (Q-W) will be
equal to the change of internal energy ΔU.
Thus, ΔU = Q – W -------------------------- (1)
This is the mathematical form of 1st law of thermodynamics.
Work done by the system and Work done on the system (W):
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Work is defined as the force applied over a distance, and it can be expressed as
W= F x d.
In the context of thermodynamics, Work done by a system is considered when there is an expansion in
volume. And in this case the work done is considered as (−) and represented as − P ΔV
W = − P ΔV
Where, P is the pressure of the system, and ΔV is the change in volume.
Work done on a system is considered when there is a compression in volume. And in this case the work done
is considered as (+) and represented as + P ΔV
W = + P ΔV
Problem 1: A gas has constant pressure in a system. There is a loss of 45 J of heat in the
surroundings around the system. 450 J of work is done on the system. Find the system’s internal
energy.
– Q = –ΔU + W
ΔU = 45 J + 450 J
ΔU = 495 J
Problem 2: Find the change in internal energy of a system if 415cal of heat is given to the system,
and the system does 35cal of work.
According to the first law, ΔU = Q – W
= 415 cal – 35 cal
= 380 cal.
Since the system does the work, and the heat is supplied to the system, it is positive.
Problem 3: If a gas of volume 30m3 is contained in a rigid container and 60J of heat is provided
to it. Then, calculate the change in internal energy. Assume that the gas exerts 1atm of pressure
on the walls.
Change in internal energy is equal to all the heat supplied. Since the container is rigid, there will be
zero volume change; therefore, the work done is zero.
Thus, ΔU = Q – W = 60 + 0 = 60J.
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❖ INTERNAL ENERGY
Internal energy is a thermodynamic property of a system that represents the sum of all microscopic forms of
energy within it, including the kinetic energy of particles (translational, rotational, and vibrational) and the
potential energy associated with the molecular structure.
It's important to note that internal energy is a state function, meaning it depends only on the current state
of the system and not on the path taken to reach that state.
Mathematically, internal energy is often denoted by the symbol U.
➢ Example:
Consider a closed container of gas. The internal energy of the gas is affected by factors like temperature,
pressure, and volume. If you heat the gas, its internal energy increases because the molecules move faster and
possess more kinetic energy.
U = ∫ (𝑇, 𝑉)
So it can be written that
(1)
At constant volume dV = 0, so the above equation can be modified as
(2)
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Again for ideal gas (dU/dV)T = 0, because ideal gas is free from any molecular interaction, so the internal
energy does not depend on the expansion or compression of the gas.
dU = n CVdT
❖ ENTHALPY
Enthalpy (H) is a thermodynamic property of a system that combines its internal energy and the product of
its pressure and volume. It is often used to describe the heat content of a system at constant pressure. The
mathematical expression for enthalpy is given by:
H=U+PV
where: H is the enthalpy, U is the internal energy, P is the pressure, V is the volume.
The change in enthalpy (ΔH) for a process occurring at constant pressure is related to the heat (q) exchanged
with the surroundings during the process:
ΔH=qp
where: ΔH is the change in enthalpy, qp is the heat exchanged at constant pressure.
ΔH=ΔU+PΔV----------------------------- (1)
However, for an ideal gas, under certain conditions, the internal energy change (ΔU) and the work done
(PΔV) can be related to the temperature change (ΔT) using the heat capacity at constant pressure (CP)
ΔU = nCv ΔT
From ideal gas equation
PV = nRT
Now at constant pressure the equation can be modified for volume and temperature change
PΔV=nRΔT
Where ‘n’ is the number of moles, Cv is the molar heat capacity at constant volume, Cp is the molar heat
capacity at constant pressure, R is the ideal gas constant (R=8.314J/(mol K)), ΔT is the temperature change.
Substituting these into the expression for ΔH in equation (1) gives:
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ΔH = n CP ΔT
This equation is particularly useful for calculating the enthalpy change of an ideal gas at constant pressure
when the temperature change is known.
CHANGE OF ENTHALPY IN A CHEMICAL REACTION:
Let us consider a reaction involving gases. If V A is the total volume of the gaseous reactants, VB is the total
volume of the gaseous products, nA is the number of moles of gaseous reactants and nB is the number of
moles of gaseous products, all at constant pressure and temperature, then using the ideal gas law, we write
Or, PΔV = Δn RT
ΔH=ΔU+ Δng RT
Note: During number of moles calculation, only the gaseous substances are to be considered.
Problem: If water vapour is assumed to be a perfect gas, molar enthalpy changes for vaporisation of 1
mol of water at 1bar and 100°C is 41kJ mol–1. Calculate the internal energy change, when
(i) 1 mol of water is vaporised at 1 bar pressure and 100°C.
(ii) 1 mol of water is converted into ice.
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∆H ≅ ∆U
so, ∆U = 41.00 kJ mol-1
❖ HEAT CAPACITY
HEAT CATACITY:
Heat capacity is defined as the amount of heat energy required to raise the temperature of a given
quantity of matter by one degree Celsius.
Heat capacity for a given matter depends on its size or quantity and hence it is an extensive property.
The unit of heat capacity is joule per Kelvin or joule per degree Celsius.
Mathematically,
Q = C ΔT
Where Q is the heat energy required to bring about a temperature change of ΔT and C is the heat capacity of
the system under study.
SPECIFIC HEAT CAPACITY:
Specific heat capacity (cs), is a measure of the amount of heat energy required to change the temperature of
a unit mass of a substance by one degree Celsius or one Kelvin. It is an intensive property, meaning that it
does not depend on the quantity of the substance but rather on its mass. The formula for calculating heat (Q)
using specific heat capacity is given by:
Q = m⋅ cs⋅ ΔT
Where, Q is the heat energy absorbed or released, m is the mass of the substance, cs is the specific heat
capacity, and ΔT is the change in temperature.
This refers to the specific heat capacity when the volume of the substance is held constant during the process.
The heat added or removed is used to change the temperature without doing work against external pressure.
Mathematically, for constant volume processes, the heat transfer is given by
Q = m⋅ Cv ⋅ΔT
This is the specific heat capacity when the pressure of the substance is held constant during the process.
The heat added or removed is used to change the temperature and also to do work against external pressure.
Mathematically, for constant pressure processes, the heat transfer is given by
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Q = m⋅ Cp⋅ ΔT.
These classifications are particularly important in the field of thermodynamics, where the behavior of
substances under different conditions is studied. The specific heat capacities at constant volume and constant
pressure are fundamental thermodynamic properties that help characterize the heat transfer processes in
various systems.
(dH/dT)P = (Q/dT)P = CP
(dU/dT)V = (Q/dT)V = CV
dU = CV dT (4)
So, combining equation (1), (2) and (3), we get
CP dT = CV dT + (P dV + V dP)
Or, CP dT - CV dT = P dV + V dP
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Reversible Process:
• A reversible process is an idealized concept in which a system undergoes changes in such a way that
both the system and its surroundings can be restored to their original states.
• At each step of the process, the system is in equilibrium with its surroundings.
• The key characteristic of a reversible process is that it can be reversed by an infinitesimally small
change in a parameter (e.g., temperature, pressure) without producing any net effect on the system or
its surroundings.
• Real-world processes are rarely reversible, as they often involve irreversibilities like friction, heat
transfer across finite temperature differences, and other dissipative effects.
Irreversible Process:
• An irreversible process is one in which the system undergoes changes that cannot be undone, and the
system and its surroundings cannot be perfectly restored to their original states.
• Irreversible processes are associated with the presence of irreversibilities, such as friction, heat transfer
across finite temperature differences, and other dissipative effects.
• The system does not remain in equilibrium with its surroundings throughout the process.
• Examples of irreversible processes include combustion, fluid flow through a pipe with friction, and
many real-world thermodynamic processes.
WORK DONE IN ISOTHERMAL REVERSIBLE PROCESS:
Let us consider ‘n’ moles of ideal gas enclosed in a cylinder fitted with a weightless and frictionless piston.
The work of expansion for a small change of volume dV against the external pressure P is given by-
dW = −P dV
∴ Total work done when the gas expands from initial volume V1 to the final volume V2, will be-
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Therefore,
At constant temperature,
P1V1 = P2V2
𝑉1 𝑃2
Or, =
𝑉2 𝑃1
Therefore,
Equation (1) & (2) are the expression for the work obtained in an isothermal reversible expansion of an ideal
gas.
WORK DONE IN ISOTHERMAL IRREVERSIBLE PROCESS:
The work done in an irreversible process can be challenging to express mathematically in a general form
because it often depends on the specific details of the process. However, for certain cases, such as a gas
undergoing irreversible expansion or compression, we can attempt to provide a simplified expression.
In the case of a gas undergoing irreversible expansion or compression against an external pressure, the work
done (W) can be expressed as the integral of the external pressure (Pext) with respect to the change in
volume (dV):
W= ∫Pext dV
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❖ ADIABATIC PROCESS
An adiabatic process is a thermodynamic process in which there is no exchange of heat with the
surroundings.
The term "adiabatic" comes from the Greek words "a," meaning without, and "diabatos," meaning transfer.
In other words, during an adiabatic process, the system undergoes a change in its internal energy without any
heat being added to or removed from the system.
For an adiabatic process, the first law of thermodynamics can be expressed as:
ΔU = Q − W
where: ΔU is the change in internal energy of the system, Q is the heat added to the system, W is the work
done by the system.
Since there is no heat exchange (Q=0), the equation simplifies to:
ΔU = −W
WORK DONE IN REVERSIBLE ADIABATIC PROCESS:
The relation between P and V in an adiabatic process for an ideal gas is
γ
PV = K (Where K is a constant)
Again from ideal gas equation it can be said that for n mole of ideal gas
P1V1 = nRT1 and P2V2 = nRT2
𝑛𝑅𝑇2−𝑛𝑅𝑇1 𝑛𝑅(𝑇2−𝑇1)
So, W =
1− 𝛾
= 1− 𝛾
--------------------------------------- (1)
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𝐶𝑝
Again, γ =
𝐶𝑣
Putting the value of γ in equation (1)
General statement: Heat flows from a body of high temperature to that with low temperature.
Clausius Statement: Heat, by itself, cannot pass from lower temperature to higher temperature.
Planck-Kelvin Statement: Heat cannot be completely converted into work. If it does so, working system
will suffer a permanent change.
❖ ENTROPY
The word ‘entropy’ means en → in; trope → transformation; that is ‘in transformation’. It is the property
related to the tendency of the system towards transformation of states.
1st law introduces internal energy (U) while 2nd law leads to the introduction of entropy (S).
➢ MATHEMATICAL EXPRESSION:
In thermodynamics, the mathematical expression for entropy (S) is often related to heat transfer (Q) and
temperature (T). For a reversible process, the change in entropy is given by the following equation:
𝑄
ΔS =
𝑇
Here, ΔS represents the change in entropy, Q is the heat transfer during the process, and T is the absolute
temperature.
For an infinitesimally small change in entropy (dS) in a reversible process, you can express it as:
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δQ
dS =
T
Here, dS is the infinitesimal change in entropy, δQ is an infinitesimal amount of heat transferred, and T is the
temperature.
It's important to note that the above expressions are applicable to reversible processes. For irreversible
processes, the change in entropy can be determined by considering the entropy production, and the concept of
entropy generation is introduced.
➢ CHANGE IN ENTROPY IN REVERSIBLE PROCESS:
Let one mole of ideal gas undergoes a change of state (T1, V1) to (T2, V2) in a reversible process. The heat
change that occurs is dqrev
ΔSrev = n 𝐶𝑣 ln 𝑇2 + n R ln 𝑉2
𝑇1 𝑉1
Here:
ΔS is the change in entropy. δQ is an infinitesimal amount of heat transferred, T is the absolute temperature.
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The inequality sign (≥) indicates that the actual change in entropy is greater than or equal to the integral on the
right side. For a reversible process, the equality holds.
❖ Work Function:
Definition: The work function is a concept primarily used in the field of solid-state physics and materials
science. It is the minimum amount of energy required to remove an electron from a solid to a point
immediately outside the solid surface.
Symbol: Usually denoted by the Greek letter phi (Φ).
Units: Electronvolts (eV) or joules (J).
Importance: The work function is crucial in understanding phenomena like the photoelectric effect, where
light falling on a material can eject electrons if its energy is greater than the work function.
❖ Free Energy:
Definition: In thermodynamics, free energy refers to the energy available to do work. It combines the internal
energy of a system with the energy associated with the system's entropy. Free energy is often used to predict
whether a process will occur spontaneously.
Types:
1. Helmholtz Free Energy (A): Used for systems at constant temperature and volume.
2. Gibbs Free Energy (G): Used for systems at constant temperature and pressure.
Equations:
For Helmholtz Free Energy:
A = U − TS
Where, U is internal energy, T is temperature, and S is entropy.
At constant temperature, the change in Helmholtz free energy can be represented as
ΔA = ΔU – TΔS
G = H − TS
Where, H is enthalpy, T is temperature, and S is entropy.
At constant temperature, the change in Gibbs free energy can be represented as
ΔG = ΔH – TΔS
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The change in free energy, ΔG, is used to determine whether a chemical or physical process is spontaneous.
If ΔG is negative, the process is spontaneous; if positive, it's non-spontaneous.
∆G gives criteria for spontaneity at constant pressure and temperature.
(i) If ∆G is negative (< 0), the process isspontaneous.
(ii) If ∆G is positive (> 0), the process is nonspontaneous.
Note : If a reaction has a positive enthalpy change and positive entropy change, it can be spontaneous when
T∆S is large enough to outweigh ∆H. This can happen in two ways;
(a) The positive entropy change of the system can be ‘small’ in which case T must be large.
(b) The positive entropy change of the system can be ’large’, in which case T may be small.
The former is one of the reasons why reactions are often carried out at high temperature.
❖ Electrochemical Cells:
Daniell cell:
Cell Reaction:
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A Daniell Cell is an ElectroChemical Cell which carries out Chemical reactions to produce Electricity.
In the Daniell Cell, Zinc metal is made of the anode, and copper metal is the cathode. The zinc anode
is dipped in Zinc salt solution and the Copper cathode is dipped in the copper salt solution. At the
anode, oxidation takes place and solid zinc converts into zinc ions. At the cathode, copper ions get
reduced to copper metal and get deposited. The Daniell Cell has a voltage of 1.1v.
➢ Cell Potential:
The driving force of the electron flow from anode to cathode shows a potential drop in the energy of
the electrons moving into the wire.
The difference in potential energy between the anode and cathode is known as the
cell potential in a voltaic cell.
(𝐸0 ) = - (𝐸0 )
𝑜𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛 𝑎𝑛𝑜𝑑𝑒 𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝑎𝑛𝑜𝑑𝑒
So the cell potential can be expressed as
𝐸0 = 𝐸0 - 𝐸0
𝐶𝑒𝑙𝑙 𝑐𝑎𝑡ℎ𝑜𝑑𝑒 𝑎𝑛𝑜𝑑𝑒
Where both are the reduction potential.
It can also be represented as
𝐸0 = 𝐸0 - 𝐸0
𝐶𝑒𝑙𝑙 𝑅 𝐿
➢ Nernst Equation:
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Mn+(aq) + n e- → M(s)
the electrode potential at any concentration measured with respect to standard hydrogen electrode
can be represented by:
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Again for the same reaction, the equilibrium constant can be represented as
[𝐶]𝑐 [𝐷]𝑑
K
c=
[𝐴]𝑎 [𝐵]𝑏
So, Nernst equation can be represented in the form of equilibrium constant as
𝑅𝑇
𝐸 = 𝐸0 - ln 𝐾
(𝑐𝑒𝑙𝑙) 𝐶𝑒𝑙𝑙 𝑐
𝑛𝐹
At 250C, the form of the equation becomes
0.059
𝐸 = 𝐸0 - log 𝐾
(𝑐𝑒𝑙𝑙) 𝐶𝑒𝑙𝑙 𝑛 𝑐
Electrical work done in one second is equal to electrical potential multiplied by total charge passed.
If we want to obtain maximum work from a galvanic cell then charge has to be passed reversibly.
The reversible work done by a galvanic cell is equal to decrease in its Gibbs energy and therefore, if
the emf of the cell is E and nF is the amount of charge passed and ∆ rG is the Gibbs energy of the
reaction, then
It may be remembered that E(cell) is an intensive parameter but ∆rG is an extensive thermodynamic
property and the value depends on ‘n’.
(1)
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➢ Acid Base:
ARRHENIUS CONCEPT:
➢ acid is a substance that gives H+ ions on dissolving in the aqueous solution. It increases the
concentration of H+ ions in the solution.
For example, hydrochloric acid in the water. HCl undergoes a dissociation reaction to
produce an H+ ion and a Cl– ion. The concentration of the H+ ions is increased by forming
hydronium ions.
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Other examples of Arrhenius acids are NHO3, H2SO4, H2PO4, H2CO3, HCOOH etc.
➢ The base is a substance that ionises OH– ion by dissolving in the aqueous solution. The
concentration of OH- ions is high in the solution.
In an aqueous solution, NaOH completely dissolves to give hydroxide ions and sodium ions,
to increase the concentration of hydroxide ions.
Some other examples of Arrhenius bases are 1st and 2nd group hydroxides, like LiOH,
Ba(OH)2, KOH, Mg(OH)2 etc.
The Arrhenius theory is applicable only in aqueous solution; for example, according to the theory,
HCl is an acid in the aqueous solution but not in benzene, even though it donates the H+ ion to the
benzene. Also, under Arrhenius’s definition, the solution of sodium amide in liquid ammonia is not
alkaline, even though the amide ion deprotonates the ammonia.
➢ Acid is a substance which donates an H+ ion or a proton and forms its conjugate base and
➢ The base is a substance which accepts an H+ ion or a proton and forms its conjugate acid.
The Bronsted-Lowry acid is a substance which donates a proton or H+ ion to another compound.
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The Bronsted-Lowry base is a substance which accepts a proton or H+ ion from other compounds.
The Bronsted-Lowry theory of an acid-base reaction involves the transfer of protons or H+ ions
between the acid and base.
Example 1:
Example 2:
➢ Lewis Acids are the chemical species which have empty orbitals and are able to accept
electron pairs from Lewis bases.
An example of such a Lewis acid would be BR3 (where R can be a halide or an organic
substituent).
➢ Lewis Bases are the chemical species which have the ability to donate an electron pair to a
given Lewis acid in order to form an adduct.
Atomic or molecular chemical species having a highly localized HOMO (The Highest
Occupied Molecular Orbital) act as Lewis bases.
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The most common Lewis bases are ammonia, alkyl amines, and other conventional amines.
Water and some other compounds are considered as both Lewis acids and bases since they can
accept and donate electron pairs based on the reaction.
Reaction Between Ag+ and Ammonia:
Here, ammonia acts as a Lewis base and the silver ion acts as a Lewis acid. Each nitrogen atom
donates an electron pair to Ag+, resulting in two separate coordinate covalent bonds. The adduct
formed from the Lewis acid and base has the chemical formula [Ag(NH3)2]+.
OXIDATION:
Oxidation can be defined as loss of electron from a chemical entity resulting either in increase in
positive charge (e.g., Zn → Zn2+ + 2 e-) or decrease in negative charge (2Cl- → Cl2 + 2e-).
REDUCTION:
Reduction can be defined as gain of electron from a chemical entity resulting either in decrease in
positive charge (e.g., Cu2+ + 2 e- → Cu) or increase in negative charge (Cl + e- → Cl-).
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In a chemical reaction there is no net loss or gain of electrons. Therefore, loss and gain of electrons
from one substance to another must take place simultaneously. In other words, in a chemical
reaction, a substance can gain electrons only if another substance which can loss electrons is also
present. This means oxidation can take place only if reduction also takes place at the same time and
vice versa.
Therefore, a redox reaction may be defined as a reaction in which electrons are
transferred from one to another reactant.
• Here oxidation state of H in H2 is 0 and that of O in O2 is at the reactant side but the
oxidation state of H in H2O is +1 and that of O in H2O is -2 at the product side.
• So, we can say that H2 is getting oxidised since its oxidation number is increasing from 0 to
+1 and is getting reduced since its oxidation number is decreasing from 0 to -2.
• The one who gets oxidised acts as a reducing agent and the one who gets reduced acts as an
oxidising agent.
• So here H2 is a reducing agent and O2 is an oxidising agent.
A Reducing agent is an agent which causes the reduction of others and themselves get oxidised
by donating electrons or by gaining oxygen.
The ones that get oxidised act as a reducing agent.
• Here oxidation state of H in H2 is 0 and that of F in F2 is 0 at the reactant side but the
oxidation state of H in HF is +1 and that of F in HF is -1 at the product side.
• So, we can say that H2 is getting oxidised since its oxidation number is increasing from 0 to
+1 and F2 is getting reduced since its oxidation number is decreasing from 0 to -1.
• The one who gets oxidised acts as a reducing agent and the one who gets reduced acts as an
oxidising agent.
• So here H2 is a reducing agent and F2 is an oxidising agent.
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➢ SOLUBILITY EQUILIBRIA:
The Solubility Equilibria are based on the assumption that the solids (electrolytes) dissolve in water
in order to give the basic particles from which they are formed.
Electrolytes are of two types: (1) strong electrolytes; (2) weak electrolytes
Strong Electrolytes: Electrolytes which are almost completely ionised into its constituent ions.
e.g., NaCl, HCl, NaOH etc.
Weak Electrolytes: The electrolytes which dissociate to small extent in its aqueous solution and
remains in equilibrium with its constituent ions in solution.
e.g., CH3COOH
Ionic Equilibrium:
Ionic equilibrium is the equilibrium which is established between the undissociated molecules and
its constituent ions in solution of a weak electrolyte.
Degree of dissociation:
The fraction of the total number of molecules which is ionised at the equilibrium state is known as
degree of dissociation. It is usually represented by the symbol α.
𝑁𝑜. 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
α=
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
𝑁𝑜. 𝑜𝑓 𝑑𝑖𝑠𝑠𝑜𝑐𝑖𝑎𝑡𝑒𝑑 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒
Percentage dissociation =
𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑐𝑢𝑙𝑒𝑠
x 100
➢ Relation between degree of dissociation(α) and equilibrium constant (K):
Let a weak electrolyte XY be dissolved in water, its ionisation may be represented as:
XY X+(aq) + Y-(aq)
Let the original concentration of XY prior to dissociation be C moles/lit and let α be the degree of
dissociation at equilibrium.
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XY X+(aq) + Y-(aq)
[𝑋+][𝑌−]
So the equilibrium constant K =
[𝑋𝑌]
𝐜𝑎 × 𝐜𝑎 𝐜𝑎𝟐
Or, K= =
𝒄(𝟏− 𝑎) 𝟏− 𝑎
Where equilibrium constant K is called dissociation constant.
If the salt is very weak in nature then degree of dissociation α<<1; and (1-α)≈ 1
𝑲
Then, K= 𝐜𝑎𝟐 and α =√
𝑪
Solubility:
Solubility can be defined as the ratio of the maximum amount of solute to the volume
of the solvent in which the solute can dissolve.
This is generally expressed in two ways i.e –
1. Grams of solute per 100 g of water
2. Moles of solute per litre of solution
A salt refers to be soluble if it dissolves in water to give a solution along with the concentration of at
least 0.1 m at the room temperature.
A salt is also considered to be insoluble if the concentration of an aqueous solution is less than
0.0001 m at the room temperature. Salts are considered to be slightly soluble; those between 0.0001
m and 0.1 m.
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Each concentration in this is raised to the power of the respective coefficient of ion in the balanced
equation. For example, the solubility product equilibrium constant for the dissociation of AgCl is:
Another example of a solubility product equilibrium constant where we can consider the reaction for
the dissociation of CaF2 in water is:
At equilibrium (1-S) xS yS
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Hardness of water
Water which does not produce lather with soap is termed as hard water. The hardness is usually
expressed in terms of Ca & Mg salts like bicarbonate, carbonate, sulphate, chloride etc.
Hard water is formed due to presence of minerals like Ca and Mg. they are not removed or
separated by sedimentation or filtration. When hard water reacts with soap (sodium salt of
stearic acid or pametic acid) gives curdy precipitate.
In above reaction hard water react with sodium salt of stearic acid to form calcium stearate or
magnesium stearate which being insoluble and separate out without producing lather.
Types of hardness
a) Temporary hardness:
Temporary hardness of water is caused by Ca and Mg bicarbonate. This can be removed
by simply boiling of water. Due to boiling bicarbonate is converted into carbonate
(insoluble precipitate)
b) Permanent hardness:
Permanent hardness is caused by the presence of soluble salt of Ca and Mg other than
bicarbonate such as chloride and sulphate. Permanent hardness cannot be removed by
boiling of water or hydrated lime. It can be eliminate by water softening techniques like
Lime-soda process, Zeolite, Ion-exchange resin, reverese osmosis etc.
Degree of hardness
The unit in which hardness is usually expressed, known as degree of hardness. Degree of
hardness is expressed in terms of calcium carbonate (CaCO3) equivalent because CaCO3
have molecular weight 100 and it is easily precipitate. Degree of hardness may be
expressed as follows-
𝑚𝑔
[𝑠𝑡𝑟𝑒𝑛𝑔𝑡ℎ 𝑜𝑓 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 ( )]×[ 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞𝑢𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓 CaCO3] ×2
Equivalent of CaCO3 = 𝑙𝑖𝑡
[ 𝑐ℎ𝑒𝑚𝑖𝑐𝑎𝑙 𝑒𝑞𝑢𝑖𝑣𝑎𝑙𝑒𝑛𝑡 𝑜𝑓 ℎ𝑎𝑟𝑑𝑛𝑒𝑠𝑠 𝑝𝑟𝑜𝑑𝑢𝑐𝑖𝑛𝑔 𝑠𝑢𝑏𝑠𝑡𝑎𝑛𝑐𝑒] ×2
OR
Unit of hardness:
i) Parts per million (ppm): it is the number of equivalent part CaCO3 present per
million (106) part of water by weight.
ii) Milligram per litre (mg/lit): it is the number of milligram of CaCO3 present in
one litre of water.
iii) Degree Clarke (oCl): it is the number of equivalent part of CaCO3 present per
70,000 part of water.
iv) Degree French (oFr): it is the number of equivalent part of CaCO3 present per 105
part of water.
Boiler Trouble
Boilers are used in industries and power station to generate steam. During conversion of
water into steam in boiler, the dissolve and suspended solids are not removed. All the
impurities are deposited in form of scale and sludge within the boiler and causes boiler
troubles.
a) Scales formation:
Scales are hard deposits, which stick on the inner wall of the boiler. These are formed
by CaCO3, CaSO4, Ca(HCO3)2, Mg(OH)2 etc. in hot portion of boiler.
b) Sludge formation:
Sludge form loose, slimy and soft precipitate in the colder area of the boiler. The
sludge formed by the CaCl2, MgCl2, MgCO3, MgSO4 etc.
i) Scales and sludge is poor conductor of heat & therefore prevent effective transfer
of heat to water.
ii) In this condition excessive heat is required which increase fuel consumption.
iii) Scale often crack due to their uneven expansion allowing the water to come
immediately in contact with overheated metal. This suddenly result in the
formation of large quantity of steam which in turn leads to excess pressure and
then to explosion.
i) Sludge formation can be removed by blow down operation. In this case impurities
can be removed by an outlet present at the bottom of boiler.
ii) Scale formation can be prevented by internal treatment that involve addition of
chemical to the boiler water either to ppt the scale forming impurities in the form
of sludge so that they can be removed by blow down method or to convert them
into soluble compounds.
a) Calgon treatment:
Calgon is sodium meta hexa phoaphate, which can be used to covert CaSO4 into
soluble complex.
Na2[Na4(PO3)6] + 2CaSO4 Na2[Ca2(PO3)6] + 2Na2SO4
Calgon soluble
b) Phosphate treatment:
Scale formation can be removed by adding sodium phosphate, which reacts with
hardness of water and form soft sludge of Ca and Mg phosphates which can be
removed by blow-down operation.
a) Zeolite process
Regeneration:
Exhausted zeolite can be regenerated by treating it with brine solution (10% NaCl
solution)
(Ca2+/Mg2+) Ze + NaCl Na2Ze + CaCl2 (or) MgCl2
Exhausted Zeolite on washing with cold water, CaCl2 & MgCl2 can be removed and
regenerated zeolite is this ready to be reused.
b) Ion-exchange resin:
In this process cations and anions are completely removed by passing impure water
into two different columns. First column contain sulphuric acid resin with acidic
group –SO3H. This column is known as cation exchange resin because it exchange
only cations like Ca2+, Mg2+, Na+ etc.
Whereas, second column contain resin with basic group like –𝑁𝑅3+ 𝑂𝐻−. It is known
as anion exchange resin because it exchanges anions like 𝐶𝑙−, 𝑆𝑂2−
4 etc.
resin–𝑁𝑅+ 𝑂𝐻− + 𝐶𝑙− resin–𝑁𝑅+ 𝐶𝑙− + 𝑂𝐻−
3 3
The removal of H+ ions from the first column and 𝑂𝐻− ions from the second column
react to form water.
Regeneration:
when both the column are exhausted, then first and second column are treated with
dilute sulphuric acid or HCl (generate H+ ions) and aqueous NaOH (generate OH–
ions) respectively. So, they have to be regenerated.
In this process, hydrated lime & sada ash use to remove hardness from water.
i) Hydrated lime:
Hydrated lime is used to remove temporary hardness of water. It react with Ca(HCO3)2 &
Mg(CO3)2 to form insoluble precipitate of calcium carbonate and magnesium hydroxide
respectively.
Hydrated lime is also used to remove permanent hardness (magnesium salt impurities
only) from water. It reacts with MgSO4 & MgCl2 to form insoluble precipitate of
magnesium hydroxide.
In above reaction calcium based impurities like CaCl2 & CaSO4 also form, which are
soluble in water. Therefore calcium based impurities (CaCl 2 & CaSO4) are not removed
by lime treatment.
The amount of lime-sada required for the softening of hard water can be calculated
by following formula-
Lime requirement = 74
[temporary hardness of Ca + 2 × temporary hardness of
100
d) Reverse osmosis:
The minimum excess pressure yhat has to be applied on the solution to prevent the
entry of the solvent molecule (pure water) into solution through semi permeable
membrane is known as osmotic pressure (lower concentration to higher
concentration).
If a pressure higher than the osmotic pressure is applied on the solution, the solvent
(pure water) will flow reverse, higher concentration solution to low concentration
solution, the process is known as reverse osmosis.
Reverse osmosis process can also be used in purification of sea water, for this purpose
sea water is delivered under pressure through the semi-permeable membrane where
water permeate the minute pores of the membrane & is delivered as purified water.
Advantages:
1) Reverse osmosis system have low maintenance requirement.
2) It removes colloidal silica, which is not removed by demineralization.
3) RO system required less energy as compare to other technology.
4) The reverse osmosis is gaining ground at present for converting sea water into
drinking water and for obtaining water for very high pressure boilers.
Phase rule
Phase rule (Willard Gibbs in 1874), play an important role to know the behavior of
heterogeneous system whereas as law of mass action is apply to know the behavior of
homogenous system. If the equilibrium between any numbers of phases is not influenced
by gravitational/electrical/magnetic forces but is influenced by pressure, temperature and
concentration, then the number of degrees of freedom (F) is related to the number of
components (C) and the number of phases (P) as:
F=C−P+2
2) Component (P):
Component is defined as “number of independent variable like temperature, pressure
and concentration by means of which composition of each phase can be expressed in
terms of chemical equation”.
F=C-P+2
Where,
F=0 (Invarient)
F=1 (Univarient)
F=2 (Bivarient)………& so on
F𝖺𝐶
1
F𝖺
𝑃
Water exists in 3 possible phases, namely solid ice, liquid water and water-vapour.
Hence, there can be three forms of equilibria, each involving two phases such as.
Solid Ice Liquid Water
Liquid Water Water-vapour
Solid Ice Water-vapour
The phase diagram for the water system is as follows and it contains curves, areas, and
triple point.
Curve OA
The curve OA is called vapourisation curve, it represents the equilibrium between
water and vapour. At any point on the curve the following equilibrium will exist.
Curve OB
The curve OB is called sublimation curve of ice, it represents the equilibrium between
solid ice and water-vapour. At any point on the curve the following equilibrium will
exist.
Solid Ice Water- vapour
This equilibrium (i.e.line OB) will extend up to the absolute zero (− 273°C).
Beyond absolute zero only solid ice will exist and no water-vapour.
Curve OC
The curve OC is called melting point curve of ice, it represents the equilibrium
between ice and water. At any point on the curve the following equilibrium will
exist.
The three curves OA, OB and OC meet at a point „O‟, where three phases namely
solid ice, liquid water and water-vapour are simultaneously at equilibrium. This
point is called triple point, at this point the following equilibrium will exist
At this point the no. of phases (P) is 3, component(C) is 1 and the degree of
freedom of the system is zero i.e., nonvariant. This is predicted by the phase rule:
F = C − P + 2; F = 1 − 3 + 2; F = 0
This takes place only at a constant temperature (0.0075°C) and pressure (4.58 mm
of Hg).
Areas
Areas AOC, BOC, AOB represent liquid water, solid ice and water-vapour
respectively where the no. of phases (P) and component(C) are one. Hence the
degree of freedom of the system is two i.e., bivariant. This is predicted by the
phase rule:
F = C − P + 2; F = 1 − 1 + 2; F = 2
Therefore, both temperature and pressure must be fixed to define the system at any
point in the areas.
B.Tech
DISSOLVED OXYGEN
Dissolved oxygen (DO) refers to the amount of oxygen gas (O2) that is dissolved in water. It is a
crucial parameter in aquatic environments, as oxygen is essential for the survival of various
aquatic organisms. Here are some key points about dissolved oxygen:
➢ Oxygen is vital for the respiration of aquatic organisms, including fish and other aerobic
bacteria.
➢ The concentration of dissolved oxygen directly affects the overall health and balance of
an aquatic ecosystem.
➢ Atmospheric Diffusion: Oxygen is naturally introduced into water through the air-
water interface by diffusion.
➢ Photosynthesis: Aquatic plants and algae contribute to oxygen production through
photosynthesis during daylight hours.
➢ Aeration: Mechanical processes, such as wind and water movement, can introduce
oxygen into water.
Four 300 ml BOD bottles are taken and added 10 ml of samples to two bottle and remaining
volume is filled with dilution water. In remaining two BOD bottle only dilution water is filled for
blank titration. Bottles are closed immediately with no air bubbler inside. Bottles are marked as
blank and sample. One blank and one sample is incubated of 20°C for dissolved oxygen (DO).
Incubated bottles are analyzed for DO after 5 days. The BOD of the sample is then given by
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𝐷1−𝐷2
BOD = × 𝐵 mg/lit
𝐴
where
BOD volume are reported as (BOD)5. High BOD indicates the presence of large number of
microorganism which indicates a high level of pollution in wash water Polluted water may
consume more oxygen than present in water (nearly 9 mg/liter at 20°C) which effects aquatic
life.
Importance of BOD
It is an index of the total organic content of water oxygen demanding substances in water. It is
a satisfactory method for determining the organic load of a water body, which is preferable to
the bio-chemical oxygen demand. COD is readily measurable parameter for streams and
industrial waste water studies and control of water treatment plants. The method is based on
the chemical oxidation of material in the presence of a catalyst Cr₂O72- in 50% H₂SO₄.
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A known amount of K2Cr₂O7, is added to a measured amount of the sample and the mixture is
boiled with concentrated sulfuric acid. After refluxing for two hours, the unreacted dichromate
(Cr2O72-) is determined by titration against a standard ferrous ammonium sulfate (Mohr's salt)
solution using ferroin as the indicator.
Ag2SO4 catalyzes the oxidation of straight chain aliphatic compounds, aromatic hydrocarbons
and pyridine HgSO4, ties up Cl- ions as soluble complex and prevents its interference. The
difference between the dichromate originally present (added) and the dichromate remaining
unreacted gives the amount of dichromate used for the oxidation of organic matter.
𝐵−𝐴
Therefore COD= ×9 mg/L
4×50
(𝐵−𝐴)×8×1000
= mg/L
4×50
= (B-A) × 40 mg/L
Importance of COD
1. The COD test is, therefore, widely used for measuring the pollutional strength of
domestic and industrial wastes.
2. The major advantages of COD test is that the determination is completed in 3 hours, as
compared to the 5 days required for the BOD determination.
3. COD is important in management and design of treatment plant.
4. It is used in calculating the efficiency of treatment plants and proposing standards for
discharging domestic effluents in various types of water streams.
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BOD COD
(a) BOD is the amount of dissolved oxygen (a) COD is a measure of both biologically
required by bacteria while oxidizing organic oxidisable (like glucose) as well as
matter under aerobic conditions in the waste biologically inert (like cellulose) organic
water. matter present in the waste water
(b) The BOD determination takes a long (b) It can be determined in short period of
period of 5 days. time around 2-3 hours.
(c) BOD values are useful generally in process (c) COD is important in management and
design and loading calculations, design of treatment plants because of its
measurement of treatment efficiency and rapid determination. It is used in calculating
operation stream pollution control, and in the efficiency of treatment plants and
determining the self-purifying capacity of proposing standards for discharging
streams. domestic effluents in various types of water
streams.
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Gibbs equation helps us to predict the spontaneity of a reaction on the basis of enthalpy and
entropy values directly. H.G.T Ellingham proposed the Ellingham diagram to predict the
spontaneity of reduction of various metal oxides. Ellingham diagram was basically a curve which
related the Gibbs energy value with the temperature. Gibbs energy is given as:
ΔG = ΔH – TΔS
With respect to a reaction, Gibbs energy can be related to the equilibrium constant as:
ΔGo= – RT ln K
Thus, when the reaction is exothermic, enthalpy of the system is negative, thus making Gibbs
free energy negative. Hence, we can say that the reaction will proceed in the forward direction
due to a positive value of the equilibrium constant. This law can be scaled for two different
reactions taking place in a system too. The overall reaction (combination of two reactions) will
occur if and only if net ΔG (sum of ΔG’s of both the reactions) of the two possible reactions is
negative.
• Ellingham diagram is a plot between Δf Go and T for the formation of oxides of metals. A
general reaction expressing oxidation is given by:
As is evident from the reaction, the gaseous amount of reactant is decreasing from left to right
as the product formed is solid metal oxide on the right side. Hence, we can say that molecular
randomness is also decreasing from left to right. Thus, ΔS is negative and ΔG shifts towards
higher side despite rising T. Hence, for most of the reactions shown above for the formation of
MxO (s), the curve is positive.
• Except for the processes in which change of phase takes place, each plot is a straight line. This
temperature at which change of phase takes place is indicated by a positive increase in the
slope. For example, the melting is indicated by an abrupt change in the curve in Zn, ZnO plot.
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• The metal oxide (MxO) is stable at the point in a curve below which ΔG is negative. Above
this point, the metal oxide is unstable and decomposes on its own.
• Feasibility of reductions of the oxide of the upper line by the element represented by the
lower line is determined by the difference in the two Δ r G0 values after the point of
intersection in the Ellingham diagram.
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