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UNIT-4
Classical thermodynamics: Partial molar properties, chemical potential, Gibb’s-Duhem
equation. Determination of partial molar quantities, Thermodynamics of real gases,
fugacity – determination of fugacity by graphical and equation of state methods,
dependence of temperature, pressure and composition, Thermodynamics of ideal and
non-ideal mixtures. Activity and activity coefficients.
Classical Thermodynamics
SRIMAAN
Partial molar properties are thermodynamic prperties of a mixture that describe the change in a specific
property of the mixture when a small amount of one component is added to or removed from the mixture, while
keeping the temperature, pressure, and amount of other components constant. These properties are important in
the study of solutions and mixtures in chemistry and chemical engineering. Some commonly discussed partial
molar properties include:
SRIMAAN
1. Partial Molar Volume (V): The change in volume of a mixture when a small amount of one
component is added to it, keeping temperature and pressure constant. Mathematically, it is
represented as:
V_i = ( V/ n_i)_T,P,n_j Where V_i is the partial molar volume of component i, V is the total volume of
the mixture, and n_i is the amount of component i.
SRIMAAN
2. Partial Molar Enthalpy (H): The change in enthalpy of a mixture when a small amount of one component
is added to it, keeping temperature, pressure, and the amount of other components constant. Mathematically,
it is represented as:
H_i = ( H/ n_i)_T,P,n_j Where H_i is the partial molar enthalpy of component i, H is the total enthalpy of
the mixture, and n_i is the amount of component i.
SRIMAAN
3.Partial Molar Gibbs Free Energy (G): The change in Gibbs free energy of a mixture when a small
amount of one component is added to it, keeping temperature,pressure, and the amount of other
components constant. Mathematically, it is represented as:G_i = ( G/ n_i)_T,P,n_j
Partial molar properties are useful in understanding the behavior of solutions and mixtures, particularly in
processes such as phase equilibria, chemical reactions, and separations. They provide insights into how the
addition or removal of a component affects the overall properties of the mixture.
Determining partial molar quantities involves experimental or theoretical methods to isolate the

______________
contribution of a specific component to the overall property of a mixture.Here's how partial molar quantities can
be determined:
SRIMAAN
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Experimental Methods:
1. Partial Molar Volume ( ViM ):
 Experimental Methods: Differential scanning calorimetry (DSC), densimetry, or pycnometry
can be used to measure changes in volume upon addition of a component while keeping
other variables constant.

 Calculation: The change in volume upon adding a small amount of a component

(ΔV) divided by the amount of substance added (Δni) gives the partial molar volume
(ˉViMˉ).
2. Partial Molar Enthalpy ( HiM ):
 Experimental Methods: Calorimetry techniques such as differential scanning calorimetry (DSC)
or isothermal titration calorimetry (ITC) can be used to measure the heat exchanged when
adding a component.
 Calculation: The heat exchanged (q) divided by the amount of substance added (Δni) gives
the partial molar enthalpy (ˉHiMˉ).
3. Partial Molar Gibbs Free Energy (ˉGiMˉ):
 Experimental Methods: For dilute solutions, the Gibbs free energy change can be determined
using vapor pressure measurements or osmotic pressure measurements.
 Calculation: The change in Gibbs free energy (ΔG) upon adding a small amount of a
component, divided by the amount of substance added (ΔΔni), gives the partial molar Gibbs free
energy (ˉGiMˉ).
Theoretical Methods:
1. Activity Coefficients (γi):
 Experimental Methods: Experimental data such as vapor-liquid equilibrium (VLE) or activity
coefficient measurements can be used to determine activity coefficients.
 Calculation: The ratio of the partial molar property to the property of the pure substance
(→1xi→1) yields the activity coefficient (γi), which is used to calculate the partial molar property.
2. Models:
 Modeling: Thermodynamic models such as the Margules, Van Laar, or Wilson models can be
employed to predict partial molar properties based on experimental data and molecular
interactions.

3. Computer Simulations:
 Simulation Methods: Molecular dynamics (MD) simulations or Monte Carlo simulations can be
used to calculate partial molar properties by simulating the behavior of individual molecules within a
mixture.

4. Derivative Approaches:
 Mathematical Analysis: Mathematical derivatives of equations describing the overall properties of
the mixture with respect to changes in the amount of a specific component can yield partial molar
properties.

______________
In practice, a combination of experimental measurements, theoretical models, and computational
simulations is often employed to accurately determine partial molar quantities for various
components in a mixture.

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Chemical Potential: The partial molar gibbs free energy has been given a specific
symbol 𝜇 because of its univerasality in dealing with various aspects of thermodynamics
studies. Its signifecance is discussed here. For a multicomponent system, free energy is a
function of T,P and number of moles (ni) of various specis.
𝜕𝐺
Thus, G= 𝑓(𝑇, 𝑃, 𝑛1, 𝑛2 , … 𝑛𝑖 ) And 𝑑𝐺 = ( )
𝜕𝑇 𝑃,𝑛
𝜕𝐺 𝜕𝐺
dT + ( ) dP + ( ) 𝑑𝑛1 + ⋯
1 ,𝑛2
𝜕𝑃 𝑇,𝑛1 ,𝑛2 𝜕𝑛1 𝑇,𝑃,𝑛
2

𝜕𝐺 𝜕𝐺
=( ) dT + ( ) dP + ̅̅̅ ̅̅̅2 d𝑛2 +….. -----(1)
𝐺1 d𝑛1 + 𝐺
𝜕𝑇 𝑃,𝑛1 ,𝑛2 𝜕𝑃 𝑇,𝑛1 ,𝑛2

Where

𝜕𝐺
̅̅̅
𝐺1 = ( ) = 𝜇𝑖, --------(2)
𝜕𝑛𝑖 𝑇,𝑃,𝑛 𝑗≠𝑖
𝑗

It is intensive property and is a meassure of escaping tendency. For a closed system 𝑑𝑛1 =
𝜕𝐺
0, 𝑑𝑛2 = 0 and equation (1) gives (𝑑𝐺)𝑁 = ( )
𝜕𝑇 𝑃,𝑛
𝜕𝐺
𝑑𝑇 + ( ) 𝑑𝑃----------(3)
𝑖
𝜕𝑃 𝑇,𝑛𝑖
But for a closed system

dG= -SdT + VdP -----------(4)

Comparing the coefficient in the equation (3) and (4) we get,

𝜕𝐺 𝜕𝐺
( ) = −𝑆, ( ) = 𝑉----------(5)
𝜕𝑇 𝑃 𝜕𝑃 𝑇

From the equation (1),(2) and (5) we have dG = -S dT + V

dP + 𝜇1 𝑑𝑛1 + 𝜇2 𝑑𝑛2 + ⋯

= -SdT + Vdp+ ∑ 𝜇𝑖 𝑑𝑛𝑖 ---------(6)

𝑖
dG = ∑ 𝜇𝑖 𝑑𝑛𝑖
𝑖

= 𝜇1𝑑𝑛1 +𝜇2𝑑𝑛2 + …. -------(7)

______________
G= 𝜇1𝑛1 +𝜇2 𝑛2 +---------- = ∑𝑖 𝜇𝑖 𝑑𝑛𝑖 ---------(8)

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(Chemical Potential)

The total differencial of G is given by

dG = 𝜇1 𝑑𝑛1+𝑛1 𝑑𝜇1 + 𝑛2 𝑑𝜇 2 +𝜇2𝑑𝑛2 -----------(9)

Comparing equn. (6) and (9) we get

-S dT + VdP + ∑𝑖 𝜇𝑖 𝑑𝑛𝑖 = 𝜇1𝑑𝑛1 +𝑛1𝑑𝜇1 + 𝑛2 𝑑𝜇 2 +𝜇2 𝑑𝑛2

= 𝜇1𝑑𝑛1 + 𝜇2 𝑑𝑛2 + 𝑛1 𝑑𝜇1 + 𝑛2 𝑑𝜇 2

-S dT + VdP + ∑𝑖 𝜇𝑖 𝑑𝑛𝑖 = ∑𝑖 𝜇𝑖 𝑑𝑛𝑖 + ∑𝑖 𝑛𝑖 𝑑𝜇𝑖

𝑖
Terms getting cancel and we get Or -S dT + VdP - ∑𝑖 𝑛𝑖 𝑑𝜇𝑖 = 0-------- (10)
∑𝑖 𝑛𝑖 𝑑𝜇𝑖 = 0
-S dT + VdP = ∑ 𝑛𝑖 𝑑𝜇𝑖
Variation of temperature on chemical potential
Chemical potential of i th component of a system is defined as
𝜕𝐺
𝜇𝑖 = ( ) --------(1)
𝜕𝑛𝑖 𝑇,𝑃,𝑛
𝑗
Differenciating equation(1) wrt T at constant P and composition we get
𝜕𝜇𝑖 𝜕 𝜕𝐺
( ) = [( ) ]
𝜕𝑇 𝑃,𝑛𝑖 𝜕𝑇 𝜕𝑛𝑖 𝑇,𝑃,𝑛
𝑗 𝑃,𝑛𝑖
2 2
Since G is a state function 𝜕 𝐺 𝜕 𝐺
=
𝜕𝑇𝜕𝑛𝑖 𝜕𝑛𝑖 𝜕𝑇
𝜕𝜇𝑖 𝜕 𝜕𝐺
∴( ) = [( ) ]
𝜕𝑇 𝑃,𝑛𝑖 𝜕𝑛𝑖 𝜕𝑇 𝑃,𝑛𝑖
𝑇,𝑃,𝑛𝑗

𝜕
= − (𝑆) 𝑇,𝑃,𝑛𝑗 = −𝑆̅𝑖 --------- (2)
𝜕𝑛𝑖
𝜕𝑆
Where 𝑆̅𝑖 = ( ) = Partial molar entropy. 𝑆 𝑔 > 𝑆 𝑙 > 𝑆 𝑠 .
𝜕𝑛𝑖
𝑇,𝑃,𝑛𝑗
Variation of Pressure on chemical potential ;
Chemical potential of i th component of a system is defined as
𝜕𝐺
𝜇𝑖 = ( )
𝜕𝑛𝑖

̅𝑖 dP
∫ 𝑑𝜇𝑖 = ∫ 𝑉
Equation (3) can be used to calculate the chemical potential of the gases, liquids and solids ,

______________
provide we know the pressure dependence of volume.

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Gibbs-Duhem equation
The Gibbs-Duhem equation is a fundamental relation in thermodynamics that describes the
behavior of extensive properties of a thermodynamic system. It states that for any mixture of chemical
substances at equilibrium, there exists a linear relationship between changes in the intensive
properties of the system.
Let's start with the expression of the Gibbs free energy G for a system of constant temperature and
pressure: G=H TS
For a system containing N moles of substances, we can express G in terms of the chemical potential
μi for each component:
G= ∑ =1
μi = (∂G/∂ni)T,P

Now, differentiate the Gibbs free energy expression with respect to the number of ni:

dG = (∂μi/∂ni)T,P dni + μidni

∑
=1
∑=1

Since the total number of moles is constant,

∑ dni=0, so we have: dG = ∑ (∂μi/∂ni) T,P dni
∂μi/∂ni = (∂μi/∂xi)T,P =1
=1

dG = (∂μi/∂xi)T,Pdxi
∑=1
Gˉi = (∂G / ∂ni )T,P
Gˉidni
dG = ∑
=1

xi = ni / ni
∑ =1
dni = ndxi+xidn
dG = Gˉi(ndxi+xidn)
∑ =1
dG = n Gˉidxi + xiGˉidn
∑ =1
∑ =1
dG = n Gˉidxi + xiμidn
∑ =1
∑=1
μi = Gˉi + RT lnxi

dG = Gˉidxi + xi(Gˉi+RTlnxi)dn
∑ ∑
______________ =1 =1

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dG = n Gˉidxi + xiGˉidn + RT xilnxidn Since xidn = dn, we have:

∑ ∑ ∑ ∑
=1 =1 =1
=1

dG=n Gˉidxi + xiGˉidn + RTdn xilnxi

∑=1
∑ =1
∑
=1

dG = n Gˉidxi + xilnxi
∑
=1
∑=1
dG = (Gˉi+RTlnxi)dxi
∑
=1

dG = μidxi
∑
=1
Therefore, the Gibbs-Duhem equation is:

μidxi = 0
∑=1

This equation states that for any mixture of chemical substances at equilibrium, there exists a linear
relationship between changes in the intensive properties of the system.

Fugacity:
Fugacity is a concept in thermodynamics and statistical mechanics that represents an effective measure of
the escaping tendency or escaping tendency per particle of a substance from a non-ideal mixture or solution. It
is often denoted by the symbol f or fi for a specific component i in a mixture. Fugacity is particularly useful in
describing non-ideal gases and solutions, where the pressure or concentration does not directly correspond to
the escaping tendency of the substance.

Escape Tendency: Fugacity represents the escaping tendency of a substance from a mixture or
solution. It accounts for deviations from ideal behavior due to interactions between molecules or
particles.
Non-Ideal Systems: In non-ideal systems, the fugacity of a component may differ from its partial
pressure or concentration. This is because the activity coefficient, which reflects the deviation from
ideal behavior, modifies the fugacity.
Relation to Pressure and Chemical Potential: In an ideal gas or solution, fugacity is equal to
pressure or chemical potential. However, in non-ideal systems, the relationship between fugacity,

______________
pressure, and chemical potential becomes more complex and is governed by equations such as the
Van der Waals equation or activity models.

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Fugacity Coefficient: In some contexts, especially in thermodynamics, the fugacity coefficient (φ) is
used. It relates the fugacity of a substance to its ideal pressure or concentration. For an ideal gas or
solution, the fugacity coefficient is equal to 1.
Units: Fugacity has the same units as pressure (e.g., pascals, atmospheres) or concentration (e.g., moles
per cubic meter).
Calculation: Fugacity can be calculated using various equations of state or activity models, depending
on the nature of the system and the level of approximation required.
Importance of Fugacity:
 Fugacity plays a crucial role in understanding and predicting the behavior of nonideal systems,
including phase equilibria, chemical reactions, and separation processes.
 It is particularly relevant in industries such as chemical engineering, where accurate predictions of
thermodynamic properties are essential for process design and optimization.
Overall, fugacity provides a more accurate description of the escaping tendency of substances in
nonideal systems compared to pressure or concentration alone, making it a valuable concept in
thermodynamics and statistical mechanics.
Measuring fugacity directly can be challenging because it is a concept used to describe the escaping
tendency of a substance from a non-ideal mixture or solution, rather than a directly measurable
quantity. However, there are indirect methods and techniques used to estimate or infer fugacity in
various experimental settings. Here are some approaches:

1. Equations of State (EOS):

 Fugacity can be calculated using equations of state such as the Van der Waals equation, Redlich-
Kwong equation, or Peng-Robinson equation. These equations relate fugacity to pressure, volume,
temperature, and the properties of the substance.
 Experimental data, such as pressure-volume-temperature (PVT) measurements, can be used to fit
parameters in these equations, allowing for the determination of fugacity.
2. Activity Coefficients:
 In the context of solutions, fugacity can be related to activity coefficients through activity models
such as the Van Laar equation, Wilson equation, or NRTL equation. These models describe
deviations from ideal behavior in terms of activity coefficients, which affect the fugacity of each
component.
 Experimental measurements of vapor-liquid equilibria (VLE) or osmotic pressure can be used to
determine activity coefficients, which can then be used to calculate fugacity.
3. Phase Equilibrium Measurements:
 Phase equilibrium experiments, such as vapor-liquid equilibrium (VLE) measurements or liquid-
liquid equilibrium (LLE) measurements, provide valuable data for estimating fugacity.
 By measuring the composition of phases in equilibrium and applying phase equilibrium models,
fugacity coefficients and fugacities can be estimated.
4. Empirical Correlations:
 Empirical correlations based on experimental data or theoretical models can provide estimates of
fugacity in specific systems or conditions.
 These correlations may be based on regression analysis of experimental data or derived from

______________
theoretical considerations.
5. Theoretical Models:
 Quantum chemical calculations or molecular simulations can provide insights into intermolecular
interactions and their effects on fugacity.
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 Computational methods such as density functional theory (DFT) or Monte Carlo simulations can be
used to predict fugacity in complex systems.
Ternary Systems
Ternary phase diagrams are graphical representations used to understand the behavior of a system
composed of three components. These diagrams are commonly used in materials science, chemistry,
and metallurgy to depict the phase relationships between the components at various combinations of
temperature, pressure, and composition.
Here's a general explanation of how ternary phase diagrams work and what they depict:
1. Components: A ternary phase diagram represents a system composed of three components. These
components could be elements, compounds, or mixtures.
2. Axes: Ternary phase diagrams typically have three axes. Each axis represents the composition of one
of the components. These compositions are usually expressed as fractions or percentages of the total.
3. Phases: The different phases of the system, such as solid, liquid, and gas, are represented within the
diagram. Boundaries between these phases are shown as lines or curves.
4. Phase Regions: Each area within the diagram represents a different phase or combination of phases
that exist under specific conditions of temperature, pressure, and composition.¥
5. Phase Boundaries: Phase boundaries indicate the conditions under which two phases coexist in
equilibrium. These boundaries can include solid-solid, liquid-liquid, solid-liquid, etc.
6. Tie Lines: Tie lines are lines drawn between two points within a phase region. They indicate the
compositions of the coexisting phases at equilibrium.
7. Invariant Reactions: Points where three phase boundaries intersect are known as invariant points.
At these points, three phases coexist in equilibrium.
8. Solid Solutions: Ternary phase diagrams can also depict solid solutions, where different
components are dissolved in each other in the solid state.
9. Eutectic Points: In some ternary phase diagrams, eutectic points may exist. These are points where
a mixture of three components melts at the lowest possible temperature.
When interpreting a ternary phase diagram, it's essential to understand the behavior of the system
under different conditions and how changes in temperature, pressure, or composition affect the phase
relationships. Additionally, experimental data and theoretical models are often used to construct and
interpret ternary phase diagrams accurately.
 Each apex represents one component of the system (A, B, and C).
 The sides connecting the apexes represent binary phase boundaries between pairs of components.
 The central region represents the ternary phase space, where all three components coexist.
 The lines and curves within the diagram represent phase boundaries and tie lines, indicating
regions of phase equilibrium and phase compositions.
 The symbols inside the phase regions indicate the phases present in those regions (e.g., liquid, solid,
gas).
Please note that the actual appearance and details of a ternary phase diagram can vary significantly
based on the specific properties and interactions of the components involved. Real-world ternary
phase diagrams are often more complex and may require professional software or experimental data
to construct accurat.
Thermodynamics of ideal and non-ideal binary systems Ideal Binary Systems:
An ideal binary system is a theoretical concept that simplifies the analysis of mixtures. In an ideal binary
system:
1. No Interactions Between Molecules: Molecules of different components do not interact with each

______________
other, meaning there are no attractive or repulsive forces between them.
2. Mixing is Energetically Neutral: Mixing of the components does not result in any energy changes.
3. Raoult's Law Applies: Raoult's law states that the partial vapor pressure of each component in the

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mixture is directly proportional to its mole fraction in the liquid phase and the vapor pressure of the
pure component. Mathematically, for an ideal binary mixture:
P i = xiPi∗
4. Ideal Behavior is Observed at All Compositions and Temperatures: This means that the behavior
of the mixture is predicted perfectly by Raoult's law.
Non-Ideal Binary Systems:
Non-ideal binary systems exhibit deviations from ideal behavior due to molecular interactions
between different components. There are two types of deviations:
1. Positive Deviation: In a positive deviation from Raoult's law, the observed vapor pressure of the
mixture is higher than predicted by Raoult's law. This typically occurs when molecules in the mixture
have stronger attractions for each other than for themselves. It often happens in mixtures containing
dissimilar molecules.
2. Negative Deviation: In a negative deviation, the observed vapor pressure of the mixture is lower
than predicted by Raoult's law. This occurs when the intermolecular attractions between different
molecules are weaker than those within individual pure components. This often occurs in mixtures
where components are similar in nature.
Thermodynamics of Non-Ideal Binary Systems:
1. Gibbs Free Energy: For non-ideal mixtures, the Gibbs free energy (G) of mixing differs
from ideal behavior. The excess Gibbs free energy (GE) is introduced to account for this difference. For
a binary mixture:
G = Gideal + GE
2. Activity Coefficients: Activity coefficients (γi) are introduced to quantify deviations from ideal
behavior. They are defined as:
μi = μiideal + RT lnγi
3. Phase Equilibria: Non-ideal mixtures may exhibit different phase behaviors compared to ideal
mixtures. Phase diagrams for non-ideal mixtures may show azeotropes or immiscibility regions, which
are not observed in ideal mixtures.
4. Activity Models: Various activity models, such as Margules, Van Laar, and Wilson models, are used
to correlate and predict activity coefficients for non-ideal mixtures based on experimental data.
Henry's Law describes the solubility of a gas in a liquid at a constant temperature, under conditions
where the gas does not react chemically with the solvent. It states that the concentration of a gas
dissolved in a liquid is directly proportional to the partial pressure of that gas above the liquid. This law
is typically expressed mathematically as:
C = kH⋅P
For an ideal binary system, Henry's Law can be applied to each component separately. Let's
consider a binary system consisting of components A and B, where A is the gas being dissolved in the
liquid solvent:
CA = kHA⋅PA
CB = kHB⋅PB
In an ideal binary system, the behavior of the components is independent of each other, so each
component follows Henry's Law independently. This implies that the solubility of each gas in the liquid
is directly proportional to its own partial pressure and governed by its respective Henry's law constant.
It's important to note that Henry's Law is an approximation that holds well for dilute solutions and

______________
low to moderate pressures. For highly concentrated solutions or high pressures, deviations from
Henry's Law behavior may occur, especially in non-ideal systems.
Activity and Activity Coefficients:

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1. Activity: In thermodynamics, activity (a) is a measure of the "effective concentration" of a species in

a mixture, accounting for deviations from ideal behavior due to interactions between molecules. It is
defined as the ratio of the chemical potential of a component in a mixture to its chemical potential
in a reference state.
ai = μi / μoi
2. Activity Coefficient: The activity coefficient (γi) quantifies the deviation from ideal behavior in a
solution. It is defined as the ratio of the activity of a species to its concentration in a solution at a
given condition.
γi = ai / Ci
Standard States:
In thermodynamics, a standard state is a defined reference state used for specifying properties
such as pressure, temperature, concentration, etc., which allows for consistency and comparability
of measurements. Commonly used standard states include:
 For gases: 1 atm pressure and a specified temperature (e.g., 25°C or 298 K).
 For liquids and solids: Pure substance at a specified pressure and temperature.
 For solutions: An infinitely diluted solution (infinite dilution) under specified conditions.
Determination of Activity and Activity Coefficients:
1. Vapor Pressure Method: In this method, the activity coefficients of components in a liquid mixture
are determined by comparing the vapor pressures of the components in the mixture to those in
their pure states using Raoult's law or other vapor pressure equations.
2. Electromotive Force (EMF) Method: Also known as the electromotive force measurement
method or cell method, this technique measures the potential difference between electrodes in an
electrochemical cell containing the solution of interest. It is used primarily for determining activity
coefficients of ions in electrolyte solutions.
3. Freezing Point Depression Method: This method involves measuring the depression in the
freezing point of a solvent when a solute is dissolved in it. By comparing the observed freezing
point depression to the theoretical value predicted by the ideal behavior, activity coefficients of the
solute can be determined.
Significance:
 Process Design: Understanding activity and activity coefficients is crucial for the design and
optimization of chemical processes involving mixtures, such as distillation, extraction, and
crystallization.
 Equilibrium Calculations: Activity coefficients are essential for accurate predictions of phase
equilibria, chemical reactions, and other thermodynamic properties in nonideal systems.
 Correlation and Prediction: Experimental data on activity coefficients are often used to develop
thermodynamic models that can correlate and predict the behavior of complex mixtures under
various conditions.
Vapour pressure method
The vapour pressure method is a common experimental technique used to determine the activity
coefficients of components in a liquid mixture. This method involves measuring the vapor pressures

______________
of the components in the mixture and comparing them to the vapor pressures of the pure
components at the same temperature. From these measurements, activity coefficients can be
calculated using Raoult's law or other vapor pressure equations.

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Here's a general outline of the experimental procedure for the vapor pressure method:
Equipment and Materials:
1. Refrigerated Circulator: To maintain a constant temperature.
2. Pressure Transducer or Manometer: To measure vapor pressures.
3. Temperature Probe or Thermometer: To monitor temperature.
4. Glass Apparatus: Such as a vapor pressure apparatus or a vapor-liquid equilibrium
(VLE) setup.

5. Pure Samples of Components: Needed for comparison.

6. Analytical Balance: To measure sample quantities accurately.
7. Vacuum Pump: To evacuate the system and create a vacuum.
Procedure:
1. Preparation of Apparatus:
 Clean all glassware thoroughly to avoid contamination.
 Assemble the vapor pressure apparatus or VLE setup according to the manufacturer's
instructions.
 Connect the pressure transducer or manometer to the system to measure vapor pressures.
2. Calibration:

 Calibrate the pressure transducer or manometer using known reference pressures.

 Ensure that the temperature probe or thermometer is accurate and calibrated.
3. Sample Preparation:
 Weigh accurately measured quantities of each component of the liquid mixture.
 Place the samples in separate containers or compartments within the vapor pressure apparatus.
4. Evacuation:
 Evacuate the system using the vacuum pump to remove any air or impurities.
 Ensure that the system is sealed to prevent leaks.
5. Temperature Control:
 Start the refrigerated circulator and set it to the desired temperature.
 Monitor and maintain a constant temperature throughout the experiment.
6. Measurement:
 Once the system reaches the desired temperature, record the vapor pressures of the components
in the mixture using the pressure transducer or manometer.
 Repeat the measurements for different compositions of the mixture by varying the proportions of
the components.
7. Comparison:
 Compare the vapor pressures of the components in the mixture to the vapor pressures of the
pure components at the same temperature.
 Calculate the activity coefficients using appropriate equations, such as Raoult's law or other

______________
8.

vapor pressure equations.
Analysis:
Analyze the data and plot graphs of vapor pressure versus composition.

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 Use the experimental data to determine the activity coefficients of the components in the mixture.
9. Cleanup:
 Clean and dismantle the apparatus after the experiment.
 Dispose of any waste materials properly.
Data Analysis:
 Calculate the activity coefficients using the measured vapor pressures and known vapor
pressures of the pure components.
 Use appropriate equations or models, such as Raoult's law, to determine the activity coefficients.
 Plot graphs of vapor pressure versus composition and analyze the data to verify the behavior of
the mixture.
Precautions:
 Ensure that the system is properly sealed to prevent leaks.
 Handle chemicals with care and follow safety procedures.
 Maintain a constant temperature throughout the experiment.
 Calibrate all instruments and equipment accurately.
By following these steps and precautions, the vapor pressure method can provide valuable data for
determining the activity coefficients of components in a liquid mixture
Freezing point method
The determination of activity and activity coefficients using the freezing point depression
method involves measuring the depression in the freezing point of a solvent caused by the presence
of a solute. This method is particularly useful for dilute solutions and relies on the relationship
between the concentration of the solute and the freezing point depression, as described by the
equation:
ΔTf = Kf⋅m
 ΔTf is the freezing point depression, SRIMAAN
 Kf is the cryoscopic constant of the solvent,
 m is the molality of the solute.
Procedure:
1. Preparation of Solutions:
 Prepare a series of solutions with known concentrations of the solute. These solutions should
cover a range of concentrations, typically spanning from very dilute to moderately concentrated.
 Accurately measure the masses of solute and solvent needed to prepare each solution.
2. Determination of Freezing Points:
 Use a suitable apparatus, such as a Beckmann or freezing point depression apparatus, to
measure the freezing points of the prepared solutions.
 Calibrate the apparatus according to the manufacturer's instructions.
 Record the freezing points of each solution.
3. Calculation of Freezing Point Depression:
 Calculate the freezing point depression (ΔTf) for each solution by subtracting the freezing point
of the pure solvent from the freezing point of the solution.
 Ensure that the measurements are accurate and consistent.
4. Plotting the Depression vs. Molality:

______________
 Plot a graph of freezing point depression (ΔTf) versus molality (m) for the solutions.
 The resulting curve should be linear for dilute solutions according to the equation ΔTf =Kf⋅m.
 Note any deviations from linearity, which may indicate non-ideal behavior.

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5. Determination of Activity Coefficients:

 The cryoscopic constant (Kf) of the solvent is known. By plotting ΔTf versus m, you can determine
the slope of the line, which corresponds to Kf.
 From the slope and known concentration of the solute, calculate the activity coefficients using the
equation: γ = 1−Kf⋅mΔTf1
Analysis and Interpretation:
 Ideal Behavior: In ideal solutions, the freezing point depression is directly proportional to the
molality of the solute, and the plot of ΔTf versus m yields a straight line passing through the
origin.
 Non-Ideal Behavior: Deviations from linearity indicate non-ideal behavior. These deviations can
be attributed to interactions between solute and solvent molecules and are quantified by activity
coefficients.
 Activity Coefficients: Activity coefficients can be determined from the slopes of the curves and are
crucial for understanding the extent of non-ideality in the solution.
Considerations and Precautions:
 Ensure accurate measurements of masses, temperatures, and freezing points.
 Use a suitable solvent with a well-known cryoscopic constant.
 Consider the limitations of the freezing point depression method for concentrated solutions and
systems exhibiting phase separation.
 Verify the linearity of the depression vs. molality plot for dilute solutions.
By following these steps and considerations, the freezing point depression method provides a valuable
means of determining activity and activity coefficients in solution systems.
Derivation of Duhem-Margules equation
The Duhem-Margules equation is a relation used to describe the excess Gibbs free energy of mixing
for non-ideal liquid solutions. It is an empirical equation derived from the concept of activity
coefficients in binary liquid mixtures. The equation is given by:
ΔGmix /RT = x1x2(A21+A12)
Derivation:
Starting with the Gibbs-Duhem equation for a binary system:
From thermodynamic principles, the chemical potential μi can be expressed as: x1dμ1+x2dμ2 = 0
μi = μi ideal + RT lnγi

x1d(μ1ideal +RT lnγ1) + x2d(μ2ideal +RT lnγ2) = 0

x1dμ1ideal+x1RT d ln γ1 +x2dμ2ideal + x2RT d ln γ2 =0
d ln γ1 = 1/x1 (∂ lnγ1 / ∂x1)T,Pdx1
d ln γ2 = 1/x2 1( ∂ lnγ2 / ∂x2)T,Pdx2
x1dμ1ideal+x1RT 1/x1 (∂ lnγ1 / ∂x1)T,Pdx1+x2dμ2ideal + x2RT 1/x2 1( ∂ lnγ2 / ∂x2)T,Pdx2=0
μi ideal = (∂G / ∂ni )T,P = Gˉi
x1 dG1/RT+ (∂ lnγ1 / ∂x1)T,Pdx1+ x2 dG21/RT + ( ∂ lnγ2 / ∂x2)T,Pdx2=0
A12 = − 1/RT (∂lnγ1 / ∂x1)T,P

______________ A21=− 1/RT ( ∂lnγ2 / ∂x2)T,P

x1 dG1/RT+ x1A12dx1+ x2 dG21/RT + x2A12 dx2=0

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Now, dGˉi / RT = d(ΔGiE/RT) / RT = dΔGiE / RT2

where ΔGiE is the excess Gibbs free energy of component i.

x1 dΔG1E / RT2+x2 dΔG2E / RT2+x1A12dx1+ x2A12 dx2 = 0
Rearranging terms, we obtain: x1dx1+x2dx2+(A12+A21)x1x2dx1=0
(1+(A12+A21)x2)dx1+(1+(A12+A21)x1)dx2=0 SRIMAAN
∫(1+(A12+A21)x2)dx1+∫(1+(A12+A21)x1)dx2=0

x1+(A12+A21)x1x2=C1
x2+(A12+A21)x1x2=C2
ΔGmix = G− Gideal = RT lnγ1+RT lnγ2
ΔGmix = RT lnγ1+RT lnγ2 = RT ln(γ1γ2)
ΔGmix = RT ln(γ1γ2)= RTln(1+(A12+A21)x1x2)
ΔGmix / RT = ln(1+(A12+A21)x1x2)
ΔGmix / RT ≈(A12+A21)x1x2
ΔGmix / RT = (A12+A21)x1x2

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Statistical Thermodynamics
Statistical thermodynamics: Concepts of statistical thermodynamics, distinguishable and non-distinguishable
particles. Assemblies, ensembles,canonical particles. Boltzmann distribution, Bose-Einstein, Fermi-Dirac
statistics, comparison and application; kinetic theory of gases, partition function and their relation to
thermodynamic quantities, calculation for model systems.
Statistical thermodynamics is a branch of thermodynamics that deals with the statistical
behavior of a large number of particles in a system. It aims to bridge the gap between the
microscopic properties of individual particles and the macroscopic properties of the system as a whole,
such as temperature, pressure, and entropy.
Statistical thermodynamics is based on the principles of probability theory and statistical
analysis, and it plays a fundamental role in explaining phenomena observed in classical and
quantum mechanical systems.
Statistical thermodynamics provides a microscopic foundation for classical
thermodynamics and helps explain the macroscopic behavior of systems.
It is used to study a wide range of physical phenomena, including phase transitions, equilibrium
properties of gases, liquids, and solids, chemical reactions, and the behavior of complex materials.
Statistical mechanics is essential for understanding the behavior of systems at the molecular and
atomic level and has applications in various fields such as chemistry, physics, materials science, and
biology.
Here are some basic terminologies commonly used in statistical thermodynamics:
1. Ensemble: A collection of multiple copies of a system, each in different states but sharing the
same macroscopic properties like temperature, pressure, and volume.

2. Microstate: A specific configuration of the individual particles (atoms or molecules) in a system

that fully specifies its state. For example, in a gas, the positions and velocities of all the particles at
a particular instant define a microstate.
3. Macrostate: A set of macroscopic parameters that describe the overall properties of a system, such
as temperature, pressure, volume, and energy.
4. Probability Distribution: The distribution of probabilities of finding the system in different
microstates, which depends on the macroscopic conditions of the system.

5. Partition Function (Z): A fundamental quantity in statistical mechanics that encapsulates all the
information about the system's microscopic states. It is defined as the sum or integral over all
possible states of the Boltzmann factor e−βEi, where Ei is the energy of state i and β=kT1 (where k is
the Boltzmann constant and T is the temperature).

6. Boltzmann Distribution: Describes the distribution of particles over different energy levels in a
system at thermal equilibrium. It states that the probability Pi of finding a particle in a particular

______________
energy state Ei is proportional to e−βEi, where β is the inverse temperature.
7.Entropy (S): A measure of the disorder or randomness of a system. In statistical thermodynamics,

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entropy is related to the number of microstates associated with a given macrostate.

8. Free Energy: A thermodynamic potential that measures the maximum amount of reversible work
that can be extracted from a system at constant temperature and volume. In statistical mechanics,
free energy is often expressed in terms of the partition function.

In statistical thermodynamics, an ensemble is a collection of multiple copies of a system, each in

different states but sharing the same macroscopic properties like temperature, pressure, and volume.
Ensembles provide a framework for understanding the statistical behavior of systems with a large
number of particles. There are several types of ensembles, each corresponding to different conditions
under which the system is studied. Below are the main types of ensembles along with explanations
and diagrams:

Canonical Ensemble: An ensemble in statistical mechanics that describes a system in thermal

equilibrium with a heat reservoir at constant temperature and volume.

Grand Canonical Ensemble: An ensemble in statistical mechanics that describes a system in thermal
and diffusive equilibrium with a heat reservoir and a particle reservoir at constant temperature, volume,
and chemical potential.

These are just a few basic terminologies in statistical thermodynamics, and the field involves many
more concepts and terms as one delves deeper into the subject.
1. Microcanonical Ensemble:
In the microcanonical ensemble, the system is isolated, meaning it does not exchange energy or
particles with its surroundings. The system is described by a fixed total energy E, volume V, and
number of particles N.
2. Canonical Ensemble:
In the canonical ensemble, the system is in contact with a heat reservoir at constant temperature T,
but it cannot exchange energy or particles with the surroundings. The system is described by its
energy E, volume V, and number of particles N, with the total energy allowed to fluctuate.
3. Grand Canonical Ensemble:
In the grand canonical ensemble, the system is in contact with a heat reservoir and a particle
reservoir, allowing both energy and particles to exchange with the surroundings. The system is
described by its chemical potential μ, temperature T, and volume V, with both energy and number of
particles allowed to fluctuate.
Explanation:
 Each ensemble represents a different set of constraints on the system, such as fixed energy,
temperature, or chemical potential.
 Ensembles allow us to compute thermodynamic properties by averaging over all possible states of
the system consistent with the constraints of the ensemble.
 The choice of ensemble depends on the experimental conditions and the properties of interest.
Ensembles play a crucial role in statistical thermodynamics, providing a framework for

______________
understanding the behavior of systems with many particles. By considering different ensembles, we
can analyze systems under various conditions and compute thermodynamic properties relevant to
different experimental setups.

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The derivation of the Maxwell-Boltzmann distribution involves considering the statistical

mechanics of a gas of non-interacting particles in thermal equilibrium. Here's a simplified derivation:
Mathematical probability and thermodynamic probability, while sharing some common concepts,
operate within different frameworks and contexts. Let's explore each of them along with examples.
Mathematical Probability:
Definition: Mathematical probability deals with the likelihood of an event occurring in a well-defined,
non-physical setting. It is expressed as a number between 0 and 1, where 0 indicates impossibility and
1 indicates certainty.
Concepts:
1. Sample Space (Ω): The set of all possible outcomes of an experiment.
2. Event (E): A subset of the sample space, representing a collection of outcomes.
3. Probability (P): A function that assigns a numerical value to each event, representing
the likelihood of that event occurring.
Example: Consider rolling a fair six-sided die. The sample space consists of six possible outcomes: {1,
2, 3, 4, 5, 6}. The probability of rolling a 3 is (3)=16P(3)=61, assuming the die is fair.
Thermodynamic Probability:
Definition: Thermodynamic probability, also known as statistical mechanics, deals with the likelihood
of different microscopic states of a physical system given its macroscopic properties. It is used to
describe the behavior of systems consisting of a large number of particles, such as gases, liquids, and
solids.
Concepts:
1. Microstate: A complete specification of the positions and momenta of all particles in a system at a
given instant.
2. Macrostate: A description of the system in terms of its macroscopic properties, such as
temperature, pressure, volume, and energy.
3. Boltzmann Distribution: Describes the probability distribution of particles among different
energy states in a system at thermal equilibrium.
Example: Consider a system of gas molecules in a box. The macrostate of the system may be
described by its temperature, volume, and pressure. The thermodynamic probability gives the
likelihood of finding the system in a particular macrostate given its energy distribution among the
molecules.
Comparison:
 Scope: Mathematical probability applies to abstract, well-defined scenarios, while thermodynamic
probability applies to physical systems governed by statistical mechanics.
 Nature of Events: In mathematical probability, events are discrete and clearly defined, while in
thermodynamic probability, events correspond to the distribution of energy states among particles
in a system.
 Applications: Mathematical probability is widely used in fields such as gambling, statistics, and
decision-making. Thermodynamic probability is essential for understanding the behavior of
physical systems in statistical mechanics, such as gas laws, phase transitions, and chemical kinetics.
Distribution of particles

______________
The distribution of particles, whether distinguishable or non-distinguishable, plays a significant role
in various fields such as statistical mechanics, quantum mechanics, and combinatorics. Let's explore the
distribution of both types of particles:

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Distinguishable Particles:
Distinguishable particles are those that can be uniquely identified from one another.
Each particle has its own distinct properties, such as position, momentum, or energy.
1. Classical Particles:
 In classical statistical mechanics, distinguishable particles are treated as separate entities.
 The distribution of distinguishable particles follows classical statistics, where each particle can
occupy its own distinct state without restriction.
 For example, consider a box containing distinguishable classical particles. Each particle can occupy
a unique position and momentum within the box.
SRIMAAN
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2. Quantum Particles:
 In quantum mechanics, distinguishable particles are also treated as separate entities with unique
quantum states.
 The distribution of distinguishable quantum particles follows quantum statistics, such as Maxwell-
Boltzmann statistics for non-interacting particles or Fermi-Dirac/Bose-Einstein statistics for
interacting particles with integer/half-integer spin.
TO BE CONTINUED.....
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