Abstract

This report presents two interconnected experiments aimed at enhancing the precision of
laboratory practices and understanding fundamental solvent interactions. The first experiment
emphasizes volumetric calibration of laboratory glassware, such as pipettes and burettes, ensuring
accuracy, reproducibility, and adherence to industry standards. Systematic errors like thermal
expansion and parallax are identified and mitigated to improve measurement reliability. The
second experiment delves into the determination of molar volumes and excess molar volumes in
ethanol-methanol binary mixtures, using density measurements to investigate intermolecular
interactions. The findings reveal the role of hydrogen bonding and molecular packing efficiency
in driving deviations from ideal behavior. Graphical analyses support the interpretation of
experimental data, offering valuable insights into solvent-solvent interactions and their practical
implications in various scientific and industrial applications.
Experiment no.1:
Volumetric Calibration
Theory:
Volumetric calibration refers to the process of determining and verifying the volume
capacity of laboratory glassware or equipment, such as pipettes, burettes, volumetric
flasks, and measuring cylinders. The purpose of volumetric calibration is to ensure
that these instruments provide accurate and reliable volume measurements, which is
crucial for precision in experiments and measurements, especially in fields such as
chemistry, biology, pharmaceuticals, and environmental testing.
Purpose of Volumetric Calibration:
There are following purpose of volumetric calibration:
1. Ensuring Accuracy of Measurements:
Volumetric calibration ensures that the glassware or equipment measures the correct
volume as stated by the manufacturer. This is important for experiments where
precise volumes of liquids need to be measured to ensure the correctness of the results.
2. Maintaining Consistency and Reproducibility:
Calibration guarantees that volume measurements are consistent across different
instruments, lab sessions, and experiments. This reproducibility is essential when
preparing solutions, conducting titrations, or working with precise concentrations of
reagents.
3. Compliance with Industry Standards:
Certain industries, such as pharmaceuticals, food production, and environmental
testing, are required to adhere to regulatory standards for quality and safety.
Volumetric calibration ensures that equipment complies with national or international
standards (e.g., ISO, ASTM) for accuracy.
4. Reducing Experimental Errors:
Even minor deviations in volume measurements can lead to significant errors,
particularly in sensitive reactions or titrations. Calibrating volumetric glassware
reduces such errors and helps maintain the integrity of experimental results.
5. Traceability:
Calibration establishes a traceable link between the instrument’s measurement and
internationally recognized standards, ensuring the measurements are reliable and

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accepted globally. This is particularly important for scientific research, legal testing,
and quality assurance.
6. Safety:
In fields such as pharmaceuticals or medicine, accurate volumetric measurements are
critical to ensuring the safety and efficacy of drugs or treatments. Incorrect dosing or
preparation of solutions can lead to serious health risks. Calibration helps prevent
such safety concerns.
7. Optimizing Equipment Performance:
Regular calibration helps identify issues with the glassware or equipment, such as
wear and tear, which may affect the volume measurements. Early detection of such
issues ensures that the equipment is functioning correctly, improving overall lab
performance and efficiency.
Systematic Errors Affecting Volumetric Measurements
The volume occupied by a given mass of liquid varies with temperature, as does the
volume of the device that holds the liquid. 20oC has been chosen as the normal
temperature for calibration of much volumetric glassware.
Glass is a fortunate choice for volumetric ware as it has a relatively small coefficient
of thermal expansion; a glass vessel which holds 1.00000L at 15oC holds 1.00025L
at 25oC. If desired, the volume values (V) obtained at a temperature (t) can be
corrected to 20oC by use of:
V20 = Vt [1 + 0.000025 (20 - t)]
In most work, this correction is small enough it may be ignored.
However, the thermal expansion of the contained liquid is
frequently of importance. Dilute aqueous solutions have a
coefficient of thermal expansion of about 0.025%/ oC. A liter of
water at 15oC will occupy 1.002L at 25oC. A correction for this
expansion must frequently be applied during calibration
procedures.
Parallax is another source of error when using volumetric ware. Parallax error in a
pipette occurs when the user's eye is not level with the liquid's meniscus, which can
lead to an inaccurate volume measurement.
A correction for this expansion must frequently be applied during calibration
procedures. Frequently, graduation marks encircle the apparatus to aid in this.

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Types of Volumetric Calibration:
1. To Contain (TC or In) Calibration:
This type of calibration ensures that the glassware holds the exact volume of liquid
stated on its label when filled to the calibration mark. For example, a 50 mL
volumetric flask is designed to contain 50 mL of liquid at a specified temperature.
2. To Deliver (TD or Ex) Calibration:
This type of calibration ensures that the glassware delivers the correct volume of
liquid. For example, a pipette or burette is calibrated to deliver the exact volume of
liquid indicated on its label when the liquid is dispensed.
General Methodology
The general procedure for calibrating volumetric glassware involves measuring the
amount of liquid it delivers or contains compared to its nominal volume. Below is a
basic method for calibrating volumetric glassware, such as a pipette or volumetric
flask.
1. Clean the equipment: Ensure the glassware is clean and free from residues, dirt,
or oils that may affect the calibration. Rinse it with distilled water and dry it.
2. Set Up a Balance: Use an analytical balance with an accuracy of at least 0.0001 g
to weigh the liquid used in calibration.
3. Use Distilled Water: Water is used for calibration since its density is well-known
and relatively stable at room temperature. Ensure that the temperature of the water
is measured and recorded.
4. Measuring the Liquid:
➢ For "To Contain" Calibration (e.g., Volumetric Flask):
• Fill the glassware (e.g., volumetric flask) to the calibration mark with distilled
water.
• Weigh the flask and record the mass of water it contains.
• Ensure the water is at the temperature specified by the manufacturer (usually
20°C). Adjust for temperature variations if necessary.
➢ For "To Deliver" Calibration (e.g., Pipette or Burette):
• Weigh a container (e.g., beaker) before and after delivering the water from the
glassware.
• For pipettes,fill and deliver the specified volume of water and weigh container.
• For burettes, dispense a known volume and measure the change in weight.

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5. Volume Calculation: Calculate the volume delivered or contained using the
formula:
𝑉= 𝑚⁄𝜌
V = Volume (mL)
m = Mass of water (g)
ρ = Density of water (g/ml), which varies with temperature.
Ensure to apply corrections for any temperature differences if the water’s temperature
deviates from 20°C.
6. Compare with Nominal Volume: Compare the measured volume with the
nominal (stated) volume on the glassware. If the error between the measured
volume and the nominal volume is outside acceptable tolerance limits,
adjustments may be required (e.g., for pipettes or burettes, this may mean
replacing or repairing the instrument).
7. Record the Results:
Document the calibration results, including the measurements, temperature, and any
corrections applied.
Key Considerations in Volumetric Calibration:
1. Temperature Effects:
Volume measurements are temperature-dependent because the density of liquids
(such as water) changes with temperature. Calibration is often performed at a standard
temperature (e.g., 20°C), and any deviations are corrected using temperature
correction factors.
2. Accuracy of Equipment:
Calibration must be performed using precise and accurate instruments, such as an
analytical balance, and high-quality reference materials.
3. Repeated Calibration:
Calibration should be repeated regularly, depending on the frequency of use and the
criticality of measurements.
4. Meniscus Reading:
Always read the bottom of the meniscus at eye level to avoid parallax error.
5. Documentation:
Keep detailed records of the calibration process and results, including the equipment
used, the results, and any corrective actions taken.

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 Calibration of Pipette
➢ Tips for Correct Use of Volumetric Glassware Pipettes
The Pipette is used to transfer a volume of solution from one container to another.
Most Volumetric Pipettes are calibrated To-Deliver (TD); with a certain amount of
the liquid remaining in the tip and as a film along the inner barrel after delivery of the
liquid. The liquid in the tip should not be blown-out.
Once the pipette is cleaned and ready to use, make sure the outside of the tip is dry.
Then rinse the pipette with the solution to be transferred. To fill the pipette, insert it
vertically in the liquid, with the tip near the bottom of the container.
➢ Objective:
The aim of this experiment is to know the accuracy & precision of a pipette by
determining the volume of pipette used.
➢ Principle:
The density of distilled water is constant at constant temperature and pressure.
Weighing the water after it has been dispensed will reveal its volume. The gravimetric
approach is used to calibrate pipette. The precision of observations while calculating
the volume of water is influenced by the surrounding temperature, atmospheric
pressure, and relative humidity. The Z factor, which is used to calculate the volume of
water, is often created by combining these components. The accuracy and precision of
the pipette are next assessed by comparing the calculated water volume with the
theoretical value.
➢ Materials Required:
• Pipette to be calibrated
• Distilled or deionized water
• Analytical balance (minimum precision: 0.0001 g)
• Beakers or weighing containe
• Thermometer (to measure water temperature)
➢ Procedure:
1. Preparation:
• Ensure the pipette is clean and in good working condition.
• Allow the pipette, balance, and water to stabilize at room temperature.
• Verify that the analytical balance is calibrated.

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2. Set the Volume:
• Adjust the pipette to the desired test volume (e.g., maximum, 50%, and
minimum capacity).
3. Weigh the Container:
• Place the weighing container on the analytical balance and tare (zero) the
balance.
4. Pipette the Water:
• Aspirate the water into the pipette. Ensure you follow the correct technique
here.
• Pre-wet the tip by aspirating and dispensing water 2-3 times.
• Hold the pipette vertically when aspirating liquid.
• Dispense the water into the tared container.
5. Record the Weight:
• Record the weight of the dispensed water. Ensure no splashing or evaporation
occurs.
6. Repeat Measurements:
• Perform at least 10 repetitions for each volume setting to ensure statistical
reliability.
7. Calculate the Volume:
• Use the density of water at the recorded temperature to convert the weight (in
grams) to volume (in microliters or milliliters).
𝑀𝑎𝑠𝑠(𝑔)
𝑉𝑜𝑙𝑢𝑚𝑒(𝑚𝑙 ) = ⁄𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝑔⁄𝑚𝑙)

8. Compare Results:
• Compare the results to the manufacturer's specifications for accuracy and
precision.
9. Adjust the Pipette (if necessary):
• If the pipette fails to meet the specifications, adjust it using the manufacturer-
provided calibration tools or send it for professional servicing.
10. Seal and Label:
• Once the pipette passes calibration, label it with the calibration date and due
date for the next calibration.
➢ Observations and calculations:

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 • For 0 to 2ml
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

38.04𝑔+38.05𝑔+38.05𝑔
Mass of water +beaker = 3

Mass of water +beaker = 38.05g

Mass of water = 2.03g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

2.03𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 2.04ml
Now calculate error:
Error = calculated volume – given volume
Error = 2.04ml- 2.00ml
= 0.04ml
%error = 0.04⁄2 × 100
%error = 2%
• For 2 to 4ml
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

38.05𝑔+38.03𝑔+38.01𝑔
Mass of water +beaker = 3

Mass of water +beaker = 38.03g

Mass of water = 2.01g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

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 2.01𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 2.02ml
Now calculate error:
Error = calculated volume – given volume
Error = 2.02ml- 2.00ml = 0.02ml
%error = 0.02⁄2 × 100
%error = 1%
• For 4 to 6ml:
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

38.01𝑔+38.00𝑔+38.00𝑔
Mass of water +beaker = 3

Mass of water +beaker = 38g

Mass of water = 1.98g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

1.98𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 1.99ml
Now calculate error:
Error = calculated volume – given volume
Error = 1.99ml- 2.00ml
= 0.01ml
%error = 0.01⁄2 × 100
%error = 0.5%
• For 6 to 8ml
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

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 38.04𝑔+38.05𝑔+38.05𝑔
Mass of water +beaker = 3

Mass of water +beaker = 38.04g

Mass of water = 2.02g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

2.02𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 2.03ml
Now calculate error:
Error = calculated volume – given volume
Error = 2.03ml- 2.00ml
= 0.03ml
%error = 0.03⁄2 × 100
%error = 1.5%
• For 8 to 10ml
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

38.04𝑔+38.05𝑔+38.05𝑔
Mass of water +beaker = 3

Mass of water +beaker = 38.07g

Mass of water = 2.05g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

2.05𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 2.06ml
Now calculate error:
Error = calculated volume – given volume
Error = 2.04ml- 2.00ml = 0.06ml

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 %error = 0.06⁄2 × 100
%error = 3%
• For 0 to 10ml
First calculate mass:
36.02𝑔 + 36.03𝑔 +36.01𝑔
Mass of beaker = 3

Mass of beaker = 36.02g

44.1𝑔+44.5𝑔+44.3𝑔
Mass of water +beaker = 3

Mass of water +beaker = 44.3g

Mass of water = 8.28g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
8.28𝑔
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦 = ⁄0.996𝑔/𝑚𝑙

Volume = 8.31ml
Now calculate error:
Error = calculated volume – given volume
Error = 8.31ml- 10.00ml = 1.6ml
%error = 1.6⁄10 × 100
%error = 16%
Now there is error in our instrument and we need to adjust the measurements to
avoid these errors

Calibration of burette
➢ Objective
To calibrate burette whilst taking into consideration the room temperature and
pressure during the experiment.
➢ Materials Needed:
o Clean burette and Distilled water
o Analytical balance
o Beaker (for collecting water)
o Thermometer (optional, for temperature correction)
o Volumetric flask (optional, for cross-checking)

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➢ Procedure:
1. Clean the Burette:
• Wash the burette thoroughly with distilled water.
• Rinse it with the solution to be used during the calibration to avoid
contamination.
2. Setup the Burette:
• Mount the burette vertically on a stand.
• Ensure the stopcock is functioning properly and there are no leaks.
3. Zero Adjustment:
• Fill the burette with distilled water to the zero mark.
• Remove any air bubbles in the nozzle by opening the stopcock briefly.
4. Record Initial Reading:
• Ensure the meniscus is at eye level.
• Record the initial reading of the burette (should be 0 mL if filled to the top).
5. Drain a Known Volume:
• Open the stopcock to release a specific volume of water (e.g., 10.00 mL) into a
pre-weighed beaker.
6. Weigh the Collected Water:
• Weigh the beaker with the collected water using an analytical balance.
• Subtract the weight of the empty beaker to find the weight of the water.
7. Calculate the Volume:
• Use the density of water at the current temperature to convert the weight of the
water into volume.
𝑀𝑎𝑠𝑠(𝑔)
𝑉𝑜𝑙𝑢𝑚𝑒(𝑚𝑙 ) = ⁄𝐷𝑒𝑛𝑠𝑖𝑡𝑦 (𝑔⁄𝑚𝑙)

(Refer to a water density table for accurate temperature-based density values.)

8. Compare and Record:
• Compare the calculated volume with the expected volume (e.g., 10.00 mL).
• Record any discrepancies.
9. Repeat Measurements:
• Repeat the process for multiple intervals (e.g., every 10 mL up to the full
capacity of the burette).
• Average the discrepancies to determine systematic errors.

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10. Determine Correction Factor:
• If consistent errors are observed, apply a correction factor for accurate
future measurements.
• Keep a detailed record of calibration data, including date, ambient
temperature, and corrections required.
➢ Observations and calculations:
First calculate mass:
30.75𝑔 + 30.72𝑔 +30.74𝑔
Mass of beaker = 3

Mass of beaker = 30.74g

81.44𝑔+81.45𝑔+81.50𝑔
Mass of water +beaker = 3

Mass of water +beaker = 81.46g

Mass of water = 50.72g
Now calculate volume:
Temperature = 30∘C
Density of water = 0.996g/ml
Volume = 𝑚𝑎𝑠𝑠⁄𝑑𝑒𝑛𝑠𝑖𝑡𝑦

50.72𝑔
= ⁄0.996𝑔/𝑚𝑙

Volume = 50.92ml
Now calculate error:
Error = calculated volume – given volume
Error = 50.92ml- 50.00ml
= 0.92ml
%error = 0.92⁄50 × 100
%error = 1.84%

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➢ Discussion:
Calibration is the process by which a stated measure such as the volume of a container
or burette is checked for accuracy. In this experiment, 50 mL burette is about to be
calibrated. Burette calibration is necessary because the temperature and pressure in
the laboratory by the time this experiment was performed did not match the standard
temperature written on the burette.
In addition, every piece of volumetric glassware has slight variations. Therefore,
every piece of volumetric glassware must be calibrated in order to allow accurate
measurements. These errors are likely to arise from weight and volume measurement.
However, weight measurement using digital scale is less likely to contain error
compared to volume measurement using burette.
➢ Precautions:
• Do not use broken glassware's as it can injure.
• When washing take special care so that it does not break on striking wash
basin walls
• When shaking a volumetric flask, hold both neck and bottom using both hands
to prevent breakage
• Remove the stopper from volumetric flask before oven drying
• Maintain constant temperature during calibration and use calibrated weights
• At time of calibration, ensure no air bubbles are sticking to the glass walls and
no water droplets exist above the graduation mark.

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Experiment no 2 :
Determination of molar volumes and investigation of
solvent – solvent interaction from density of their
mixture.

Introduction

The determination of molar volumes and investigation of solvent-solvent interactions

in liquid mixtures provide crucial insights into the physicochemical properties of
solutions. Liquid mixtures are widely encountered in industries such as
pharmaceuticals, food processing, and petrochemicals. Understanding their behavior
is essential for process optimization, product formulation, and theoretical studies.

When two solvents are mixed, their individual molecular interactions can either
enhance or disrupt the structure of the resulting solution. These interactions lead to
changes in physical properties such as density, molar volume, viscosity, and enthalpy.
By analyzing the density of mixtures at various compositions, it is possible to
calculate molar volumes and quantify deviations from ideal behavior. This
experimental approach provides valuable information about the nature and strength of
solvent-solvent interactions.

The molar volume and related parameters such as excess molar volume help reveal
whether mixing results in strong attractive interactions (e.g., hydrogen bonding) or
weak repulsive interactions (e.g., steric effects). These volumetric studies are
particularly useful in exploring the behavior of polar, nonpolar, and hydrogen-
bonding solvents in mixtures.

Theoretical background and equations

➢ Molar Volume of a Pure Liquid

The molar volume of a pure liquid (Vm) is defined as the volume occupied by one
mole of the liquid. It is a fundamental property that can be calculated using the
equation:

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 Vm =𝑀𝜌

The molar volume provides insights into the molecular packing of the liquid and how
closely the molecules are arranged. For example, liquids with strong intermolecular
forces tend to have lower molar volumes due to denser packing, while weaker forces
result in larger molar volumes.

➢ Molar Volume of a Mixture

The molar volume of a mixture is the volume occupied by one mole of the mixture,
which is influenced by the densities and compositions of its components. It is
calculated using the equation:

Vm =∑ 𝑋𝑀
𝜌

where Xi and Mi are the mole fraction and molar mass of each component, and ρ is the
density of the mixture. Unlike pure liquids, the molar volume of a mixture depends on
the interactions between the molecules of the different components.

➢
Excess Molar Volume VE

The excess molar volume VE quantifies the deviation of the mixture’s actual molar
volume from the ideal value predicted by the individual molar volumes of its
components.

VE = (M1X1+M2X2) / ρ1,2 - (M1X1) / ρ1 - (M2X2) / ρ2

Where VE – is the excess molar volume of liquid mixture, x 1 and x2 are mole fractions,
M1 and M2 are molecular weights, V1 and V2 are the molecular volumes of
components 1 and 2 of liquid mixtures respectively and ρ 1, ρ2 and ρ1,2 are the densities
of components 1, 2 and liquid mixture respectively.The excess molar volume
indicates how molecular packing and intermolecular interactions change upon mixing.
For instance:
• Negative: Suggests strong attractive interactions (e.g., hydrogen bonding, ion-
dipole forces), leading to closer molecular packing.
• Positive: Suggests repulsive or weaker interactions, resulting in less efficient
packing and possible structural disruptions.

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➢ Solvent-Solvent Interactions

Solvent-solvent interactions refer to the intermolecular forces that occur between

molecules of different solvents in a mixture. These interactions play a crucial role in
determining the physical properties of the mixture, such as density, viscosity,
refractive index, and molar volume. The nature and strength of these interactions
depend on the polarity, hydrogen bonding capacity, and molecular structure of the
solvents involved. Strong attractive interactions, such as hydrogen bonding or dipole-
dipole forces, lead to better molecular packing, which often results in a decrease in the
volume of the mixture and a negative excess molar volume.

➢ Ethanol-Methanol System

The ethanol-methanol system is an example of a liquid mixture with strong solvent-

solvent interactions, primarily due to the formation of hydrogen bonds. Both ethanol
and methanol are polar molecules with hydroxyl groups (−OH) capable of extensive
hydrogen bonding. When mixed, the hydroxyl groups of ethanol and methanol
interact strongly, creating a network of hydrogen bonds between the two molecules.
These interactions lead to a close molecular packing in the mixture, resulting in
minimal deviation from ideal behavior.

The excess molar volume for the ethanol-methanol system is typically negative,
reflecting the attractive forces between the molecules. However, because both ethanol
and methanol have similar molecular structures, the deviation from ideality is less
pronounced compared to mixtures of solvents with very different polarities or
structures. This similarity in molecular size, polarity, and hydrogen-bonding ability
ensures compatibility between the two solvents.

Reason for Graph Deviations

The graph shows the relationship between excess volume and mole fraction for the
ethanol-methanol system. The observed points and their variations arise due to the
nature of molecular interactions between ethanol and methanol molecules at
different compositions.

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Why these points are observed:

1. Hydrogen Bonding and Molecular Packing:

Both ethanol and methanol have hydroxyl groups (−OH) capable of forming hydrogen
bonds. At specific mole fractions, the formation of hydrogen bonds between ethanol
and methanol leads to better molecular packing and a negative excess volume (e.g.,
at mole fraction ~0.2). This contraction happens because the molecules are arranged
more efficiently compared to their pure states.

2. Structural Mismatch:

At other mole fractions (e.g., around mole fraction ~0.5), the arrangement of
molecules might not be as efficient due to differences in the molecular size or the
balance of interactions. This can lead to weaker packing or small voids between
molecules, resulting in positive excess volume at these points.

3. Dynamic Interaction Changes Across Compositions:

As the mole fraction changes, the ratio of ethanol to methanol molecules changes,
altering the extent of interactions like hydrogen bonding, van der Waals forces, or
dipole-dipole forces. This interplay can cause fluctuations in the excess volume,
leading to alternating positive and negative regions.

4. Contributions of Pure Components:

At mole fractions closer to 0 or 1 (pure methanol or pure ethanol), the mixture

behaves more like the pure liquid. As a result, the deviations from ideality (and the
excess volume) diminish, approaching zero.

Specific Observations in the Graph:

• Negative peaks (around mole fraction ~0.2): Strong hydrogen bonding and
efficient packing dominate, leading to volume contraction.
• Positive peaks (around mole fraction ~0.6–0.8): Structural mismatches or
weaker interactions cause expansion in the mixture.

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 • Smooth transitions: The smooth curve indicates that the changes are due to
continuous variations in interaction strength and molecular arrangement.

The variations in the excess molar volume reflect the complex balance between
attractive and repulsive forces in the ethanol-methanol system as their relative
concentrations change. These points are the result of non-ideal behavior in the
mixture.

What happened If Density decreases only?

If the density decreases with the increasing mole fraction of methanol in the
methanol-ethanol mixture, the most likely reasons are:

1. Positive Excess Volume: The mixture may exhibit positive excess volume,
meaning the total volume of the mixture is greater than expected based on the
volumes of the pure components. This results in a larger volume and
consequently a lower density.
2. Weaker Solvent-Solvent Interactions: The interactions between methanol
and ethanol molecules might be weaker than the interactions within each
solvent in its pure form. This leads to less efficient packing of the molecules,
causing the mixture to expand, which reduces the density.
3. Molecular Size and Packing: Methanol is a smaller molecule than ethanol.
When mixed, the smaller methanol molecules may not pack as efficiently
into the spaces between the larger ethanol molecules, leading to an increase in
the total volume of the mixture, which decreases the density.

In summary, the decrease in density is likely due to a positive excess volume, weaker
interactions between methanol and ethanol, and less efficient molecular packing, all
leading to an overall increase in the volume of the mixture and a decrease in density.

Alternating pattern of density:

The alternating pattern of density decreasing and increasing with increasing mole
fraction of methanol in the methanol-ethanol mixture likely results from complex
intermolecular interactions. These interactions, such as hydrogen bonding between

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methanol and ethanol molecules, vary at different concentrations, causing changes in
the mixture's volume and, therefore, its density.

At certain mole fractions, stronger interactions lead to more compact packing and
higher density, while weaker interactions lead to expansion and lower density. The
positive and negative excess volume effects also contribute to this behavior, with
fluctuations in the total volume of the mixture as the composition changes.

In short, the oscillating density pattern reflects non-ideal mixing behavior, where the
molecular interactions and packing efficiency change as the mole fraction of methanol
varies.

Significance of excess molar volumes:

1. Insights into Molecular Interactions

Excess molar volume directly reflects the nature of forces between the molecules in a
mixture:
• Positive VE:
o Indicates repulsive forces are dominant, often due to:
▪ Incompatibility of molecular structures: When the size or
shape of molecules does not allow close packing.
▪ Weak interactions, like in mixtures of polar and nonpolar
molecules (e.g., benzene and water).
▪ Presence of bulky or branched molecules, leading to a loosely
packed structure.
o Examples: Hexane mixed with smaller, polar alcohol molecules.
• Negative VE :
o Shows attractive forces between molecules, such as:
▪ Hydrogen bonding: Common in systems like water-alcohol
mixtures.
▪ Dipole-dipole interactions: Polar molecules aligning to reduce
the overall volume.
▪ Efficient packing in mixtures where components complement
each other structurally or chemically.

19 | P a g e
 o Examples: Ethanol and water mixtures exhibit strong hydrogen
bonding, leading to significant volume contraction.
2. Characterizing Mixture Behavior
Excess molar volume quantifies the deviation of a mixture's behavior from ideality:
• In Ideal Mixtures:
o VE =0, meaning no excess interactions exist, and the volume is an
additive property.
o Such mixtures are rare in real systems.
• In Non-Ideal Mixtures:
o VE ≠0, highlighting deviations due to structural and energetic
differences between the components.
o These deviations provide insights into phenomena like clustering,
segregation, or specific interactions (e.g., ionic or covalent).
By studying VE, we can understand how components influence each other
volumetrically, aiding in predictions of other properties like viscosity, surface tension,
and diffusion.
3. Thermodynamic and Energetic Insights
Excess molar volume serves as a gateway to understanding thermodynamic behavior:
• Energy Changes:
o A positive or negative VE correlates with changes in Gibbs free energy
(GE), enthalpy (HE), and entropy (SE):
▪ Positive VE: Suggests endothermic mixing (energy absorption
due to repulsive interactions).
▪ Negative VE: Indicates exothermic mixing (energy release due
to attractive forces).
• Phase Behavior:
o Helps predict miscibility, phase separation, and azeotropic behavior.
o Used in designing processes involving liquid-liquid equilibria or
vapor-liquid equilibria.
• Nonlinear Properties:
o Provides the basis for understanding concentration-dependent
properties, such as refractive index, dielectric constant, and
compressibility.
4. Industrial Applications – Deep Dive

20 | P a g e
Excess molar volume plays a pivotal role in industrial and applied science fields. Its
applications include:
a. Chemical Process Design:
• Separation Processes:
o VE data helps optimize distillation columns, solvent extraction systems,
and crystallization processes by predicting volume changes during
phase separation.
• Reactor Design:
o Understanding volume changes in reacting mixtures ensures proper
equipment sizing and pressure control.
b. Material Science:
• Alloy and Polymer Design:
o Helps in determining miscibility and compatibility of different
materials, ensuring strength, durability, and uniformity in alloys or
polymer composites.
• Nanotechnology:
o Guides the synthesis of nanoparticles or nanofluids where molecular-
level volume interactions are critical.
c. Pharmaceuticals and Formulation Science:
• Solvent Selection:
o Helps in selecting solvents for drug delivery systems, ensuring stability
and optimal dissolution of active pharmaceutical ingredients (APIs).
• Emulsions and Suspensions:
o Predicts how components will interact to create stable formulations.
d. Petrochemical and Energy Sector:
• Fuel Blending:
o In fuels and lubricants, VE predicts the efficiency and performance of
blended hydrocarbons or biofuels.
e. Food and Beverage Industry:
• Flavor and Texture Design:
o Ensures consistent texture and taste by predicting how ingredients will
volumetrically interact during mixing.
f. Environmental Applications:
• Sustainable Process Design:

21 | P a g e
 o Assists in designing eco-friendly solvents and processes, minimizing
waste and energy use.
5. Structural and Molecular Insights
Excess molar volume reveals the structural properties and packing efficiency of
molecules:
• Void Formation:
o VE indicates whether voids or empty spaces exist in the mixture, which
could affect material properties.
• Molecular Clustering:
o Highlights whether specific molecules tend to group together due to
attractive forces, which may affect phase stability.
• Packing Efficiency:
Helps analyze the extent of molecular alignment or disorder, essential for materials
with specific structural requirements (e.g., optical materials, semiconductors)

Objective :
i. To measure the densities of pure solvents and their binary mixtures.
ii. To calculate the molar volumes and excess molar volumes of the mixtures.
iii. To investigate solvent-solvent interactions based on the excess molar volumes
and density data.

Materials Required :
i. Density bottle with known volume
ii. Analytical balance (accuracy: ±0.0001 g).
iii. Volumetric flasks (10 mL, 25 mL, 50 mL).
iv. Pipettes (1 mL, 5 mL, 10 mL).
v. Thermometer (accuracy: ±0.1 °C).
vi. Stirring apparatus (optional).
vii. Clean and dry glassware.

Chemicals Required:
i. Solvent 1: Ethanol.
ii. Solvent 2: Methanol.

22 | P a g e
 iii. Calibration standard for density bottle (e.g., distilled water).
Procedure:
A. Calibration of the Density Bottle
i. Clean and dry the density bottle thoroughly.
ii. Weigh the empty density bottle using an analytical balance and record its mass
iii. Fill the density bottle with distilled water at the experimental temperature,
ensuring there are no air bubbles.
iv. Weigh the filled density bottle and record its mass
v. Calculate the volume of the density bottle using the known density of water at
the experimental temperature
vi. Use this volume for all subsequent density calculations.
B. Measurement of Densities
i. Measure and record the densities of the pure solvents (ethanol, methanol, and
acetone) at the experimental temperature.
ii. Prepare binary mixtures of the solvents in different mole fractions. For
example: Ethanol + Methanol: 10%, 20%, 30%, ..., 90% ethanol by volume.
iii. Accurately weigh the required amounts of solvents using the analytical
balance and mix them in volumetric flasks.
iv. Fill the density bottle with each prepared mixture, ensuring no air bubbles are
present, and weigh the bottle. Record the mass of the filled bottle .
v. Calculate the density of each mixture using the formula: ρ = mass/ Vc :
vi. Repeat the density measurements three times for each sample to ensure
accuracy and precision.
C. Calculation of Molar Volumes
i. Calculate the molar volume of each mixture using the formula:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp =
𝛒𝐦𝐢𝐱

D. Determination of Excess Molar Volumes

i. Calculate the excess molar volume using:
VmE = Vm exp - Vm ther
ii. Record and tabulate the excess molar volumes for all mixtures.
E. Analysis of Results
i. Plot the excess molar volume against the mole fraction of one solvent.

23 | P a g e
ii. Analyze the behavior of the curve: A negative indicates strong attractive
interactions (e.g., hydrogen bonding). A positive indicates weaker interactions or
structural expansion.
iii. Discuss how the type and strength of interactions vary with composition and
temperature.
Calculations:
I. Calibration of density bottle:
11.58+11.58+11.59
Mass of empty bottle (m1):
3
m1 = 11.58 g
36.81+36.82+36.81
Mass of empty bottle + distilled water (m2) =
3
m2= 36.81 g
Mass of water = m2－m1 = 36.81-11.58 = 25.23 g
Now let calculate volume of water,
Volume = mass / density:
25.23𝑔
Volume =
0.997 𝑔/𝑚𝑙

Volume = 25.30 ml

II. Densities:
For Pure methanol:
Mass of empty bottle (m1) = 11.20 g
31.69+31.67+31.67
Mass of empty bottle + methanol (m2) =
3
m2= 31.68 g
Mass of methanol = m2－m1 = 31.68 g - 11.58 g = 20.1g
Now, ρ = mass/ Vc:
20.1𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.79g ml-1
For Pure ethanol:
Mass of empty bottle (m1) = 11.58 g
31.97+31.94+31.93
Mass of empty bottle + ethanol (m2) =
3

24 | P a g e
 m2 = 31.94g
Mass of methanol = m2－m1 = 31.94 g -11.58 g = 20.36g
Now, ρ = m / Vc:
20.36𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.8047 g ml-1
For Binary mixtures
• n1, X1 and M1 represents no. of moles,mole fraction of methanol and molar
mass of methanol respectively.
• n2, X2 and M2 represents mole fraction of ethanol and molar mass of ethanol
respectively
Mixture 1;
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 3.24
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.101
32
𝑚𝑎𝑠𝑠 41.06
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.898
46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.101
X1 = = 0.101
0.101+0.898
0.898
X2 = = 0.90
0.101+0.898
X1M1 + X2M2 = Mmix
0.101 × 32 + 0.901 × 46 = Mmix
3.232 + 41.446 = 44.678 g
Mass of empty bottle (m1) = 11.58 g
Mass of empty bottle + mixture = (m2) = 31.62 g
Mass of mixture = m2－m1 = 31.62g － 11.58g = 20.04g
Now , ρ = m / Vc :
20.04𝑔
ρ=
25.30𝑚𝑙
ρ = 0.792 g ml-1
Mixture 2 ;
X1M1 + X2M2 = Mmix

25 | P a g e
 𝑚𝑎𝑠𝑠 6.42
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = 32
= 0.2006
𝑚𝑎𝑠𝑠 36.80
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.80
46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.2006
X1 = = 0.20
0.2006+0.80
0.80
X2 = = 0.80
0.101+0.80
X1M1 + X2M2 = Mmix
0.20 × 32 + 0.80 × 46 = Mmix
6.4 + 36.8 = 43.2 g
Mass of empty bottle (m1) = 11.58g
31.87+31.87+31.85
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.87 g
Mass of mixture = m2－m1 = 31.87g － 11.58g = 20.29 g
Now , ρ = m / Vc :
20.29 𝑔
ρ=
25.30𝑚𝑙
ρ = 0.8019 g ml-1
Mixture 3 ;
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 9.64
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.30125
32
𝑚𝑎𝑠𝑠 32.21
n2 = = = 0.7002
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.30125
X1 = = 0.301
0.30125+0.7002
0.7002
X2 = = 0.699
0.30125+0.7002

X1M1 + X2M2 = Mmix

0.301 × 32 + 0.699 × 46 = Mmix
Mmix =41.786

26 | P a g e
 Mass of empty bottle (m1) = 11.58 g
31.84+31.82+31.75
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.82 g
Mass of mixture = m2－m1 = 31.82g － 11.58 g = 20.24g
Now , ρ = m / Vc :
20.24𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.8 g ml-1
Mixture 4:
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 12.9
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.403
32
𝑚𝑎𝑠𝑠 27.6
n2 = = = 0.6
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.403
X1 = = 0.402
0.403 + 0.60
0.6
X2 = = 0.598
0.403+0.60
X1M1 + X2M2 = Mmix
0.40 × 32 + 0.60 × 46 = Mmix
12.89 + 27.68 = 40.57g
Mass of empty bottle (m1) = 11.58 g
31.74+31.73+31.73
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.73 g
Mass of mixture = m2－m1 = 31.73 g － 11.58 g = 20.15g
Now, ρ = m / Vc:
20.15𝑔
ρ=
25.30𝑚𝑙
ρ = 0.7964 g ml-1

Mixture 5:
X1M1 + X2M2 = Mmix

27 | P a g e
 𝑚𝑎𝑠𝑠 16.02
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = 32
= 0.5006
𝑚𝑎𝑠𝑠 23.08
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.5017
46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.5006
X1 = = 0.5
0.5006+0/5017
0.5017
X2 = = 0.5005
0.5006+0.5017
X1M1 + X2M2 = Mmix
0.5 × 32 + 0.5005× 46 = Mmix
=38.991g
Mass of empty bottle (m1) = 11.58g
31.86+31.83+31.82
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.836 g
Mass of mixture = m2－m1 = 31.836 g － 11.58g = 20.2166 g
Now, ρ = m / Vc :
20.2166 𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.7990 g ml-1

Mixture 6 ;
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 19.23
n1 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.600
32
𝑚𝑎𝑠𝑠 18.6
n2 = = = 0.40
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 46
𝑛1
X1=
𝑛1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.600
X1 = = 0.60
0.40 + 0.60
0.40
X2 = = 0.40
0.40+0.600
X1M1 + X2M2 = Mmix
0.40 × 32 + 0.60 × 46 = Mmix

28 | P a g e
 19.25 +18.4 = 37.65
Mass of empty bottle (m1) = 11.58g
31.78+31.78+31.78
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.78g
Mass of mixture= m2－m1 = 31.78 g－ 11.58g = 20.20 g
Now, ρ = m / Vc:
20.20 𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.7986 g ml-1

Mixture 7:
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 22.6
n1 = = = 0.7
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 32
𝑚𝑎𝑠𝑠 13.81
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.300
46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.70
X1 = = 0.702
0.7+0.300
0.300
X2 = = 0.298
0.70+0.300

X1M1 + X2M2 = Mmix

0.298× 32 + 0.702 × 46 = Mmix
= 36.172
Mass of empty bottle (m1) = 11.58 g
31.75+31.77+31.76
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.76g
Mass of mixture = m2－m1 = 31.76g － 11.58 g = 20.18g
Now , ρ = m / Vc :
20.18𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.7976 g ml-1

Mixture 8:

29 | P a g e
 X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 25.65
n1 = = = 0.8016 mol
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 32
𝑚𝑎𝑠𝑠 9.22
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.2004 mol
46
𝑛1
X1=
𝑛1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.8016
X1 = = 0.8
0.8016+0.2004
0.2004
X2 = = 0.2
0.2004+0.8016
X1M1 + X2M2 = Mmix
0.80 × 32 + 0.2 × 46 = Mmix
25.61 + 9.20 = 34.8
Mass of empty bottle (m1) = 11.58 g
31.74+31.75+31.75
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.74g
Mass of mixture = m2－m1 = 31.74 g -11.58 g = 20.17g
Now, ρ = m / Vc :
20.17 𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.7972 g ml-1

Mixture 9:
X1M1 + X2M2 = Mmix
𝑚𝑎𝑠𝑠 28.80
n1 = = = 0.9
𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 32
𝑚𝑎𝑠𝑠 4.62
n2 = 𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 = = 0.1
46
𝑛1
X1= 𝑛
1 +𝑛2
𝑛2
X2= 𝑛
1 +𝑛2

0.9
X1 = = 0.9
0.9+0.1
0.1
X2 = = 0.1
0.9+0.1
X1M1 + X2M2 = Mmix

30 | P a g e
 0.9× 32 + 0.1 × 46 = Mmix
28.81+ 4.65 = 33.4
Mass of empty bottle (m1) = 11.58 g
31.70+31.70+31.70
Mass of empty bottle + mixture =
3
Mass of empty bottle + mixture = (m2) = 31.70 g
Mass of mixture = m2－m1 = 31.7 g – 11.58 g =20.12 g
Now, ρ = m / Vc :
20.12 𝑔
ρ=
25.30 𝑚𝑙
ρ = 0.7953 g ml-1
Table no. 2.1:
Mole fraction of methanol vs density of binary mixture (methanol + ethanol)

Mole fraction (X1) Density (g/ml)

0.1 0.804
0.2 0.802
0.3 0.800
0.4 0.7996
0.5 0.7990
0.6 0.7986
0.7 0.7976
0.8 0.7972
0.9 0.7953

Graph

0.805
y = -0.0095x + 0.8041
0.804
R² = 0.9635
0.803
density (g/ml)

0.802
0.801
0.8
0.799
0.798
0.797
0.796
0.795
0.794
0 0.2 0.4 0.6 0.8 1
mole fraction of methanol (X1)

Graph no. 2.1: density vs mole fraction of methanol

31 | P a g e
Graph Fitting:
The equation in this graph represents the relationship between experimental density
(on the y-axis) and the mole fraction of methanol (on the x-axis).
It shows a linear relationship between density (g/mL) and the mole fraction of
methanol (X), represented by the equation:
y=−0.0095x+0.8041
Where:
• y: Density (g/mL)
• x: Mole fraction of methanol

Explanation of the Equation

1. Slope (−0.0095):
o This value represents the rate of change of density with respect to the
mole fraction of methanol.
o A negative slope indicates that as the mole fraction of methanol
increases, the density decreases.
o For every unit increase in mole fraction of methanol, the density
decreases by 0.0095 g/mL.
2. Intercept (0.8041):
o This is the density value when the mole fraction of methanol (xx) is
zero. In this context, it represents the density of the solvent (likely
water or a mixture without methanol).
3. R-squared Value (R2=0.9635)
o This metric shows how well the linear equation fits the data.
o A value of 0.9635 indicates that 96.35% of the variation in density can
be explained by the mole fraction of methanol, meaning the fit is very
good.

Physical Interpretation

• As methanol is mixed with the solvent which is ethanol here, its mole fraction
increases, and the overall density of the mixture decreases.
• This trend is typical in binary liquid mixtures where methanol (less dense)
replaces water or another denser liquid i.e ethanol.

32 | P a g e
Table no. 2.2:
Mole fraction of ethanol vs density of binary mixture (methanol+ ethanol)

Mole fraction of ethanol (X2) Density (g/ml)

0.9 0.804

0.8 0.802

0.7 0.800

0.6 0.7996

0.5 0.7990

0.4 0.7986

0.3 0.7976

0.2 0.7972

0.1 0.7953

Graph no. 2.2

0.805
0.804
y = 0.0095x + 0.7946
0.803 R² = 0.9635
Density (g/ml)

0.802
0.801
0.8
0.799
0.798
0.797
0.796
0.795
0.794
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
Mole fraction of ethanol(x2)
Graph no. 2.2: density vs mole fraction of ethanol

33 | P a g e
This graph shows a linear relationship between density (g/mL) and the mole fraction
of ethanol (X2), represented by the equation:
y=0.0095x+0.7946

Where:

• y: Density (g/mL)
• x: Mole fraction of ethanol

Explanation of the Equation

1. Slope (0.0095):
o This value indicates the rate of change of density with respect to the
mole fraction of ethanol.
o A positive slope suggests that as the mole fraction of ethanol increases,
the density increases.
o For every unit increase in the mole fraction of ethanol, the density
increases by 0.0095 g/ml.
2. Intercept (0.7946):
o This is the density value when the mole fraction of ethanol (x 2) is zero.
It represents the density of the base solvent (likely pure water or a
different liquid without ethanol).
3. R-squared Value (R2=0.9635):
o This indicates how well the linear equation fits the data.
o A value of 0.9635 means 96.35% of the variation in density is
explained by the mole fraction of ethanol, showing a very good fit.

Physical Interpretation

• As ethanol is mixed with the solvent, its mole fraction increases, and the
overall density of the mixture also increases.
• This trend is expected in mixtures where ethanol (which is denser) is added to
a lighter solvent.

34 | P a g e
 Experimental Molar volumes
For Pure methanol :
ρ = m / Vm
Molar mass
Where’s 𝑉𝑚1 =
ρ
32
𝑉𝑚1 = = 40.506 ml
0.79

For Pure ethanol :

ρ = m / Vm
Molar mass
Where’s 𝑉𝑚2 =
ρ
46
𝑉𝑚2 = = ml
0.80
Mixture 1:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp =
𝛒𝐦𝐢𝐱
0.1 × 32 + 0.9 × 46
Vm ex p = 0.803
44.678
Vm ex p = = 55.549ml
0.803
Mixture 2:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp= 𝛒𝐦𝐢𝐱
0.20 × 32 + 0.8 × 46
Vm ex p = 0.802
6.4+36.8
= = 53.865 ml
0.802
Mixture 3
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp= 𝛒𝐦𝐢𝐱
0.301 × 32 + 0.699 × 46
=
0.800
9.632+32.2
=
0.800

= 52.2325 ml
Mixture 4 ;
X1M1 + X2M2
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp=
𝛒𝐦𝐢𝐱
0.402× 32 + 0.598 × 46
= 0.7996

35 | P a g e
 40.48
=
0.798

= 50.490ml
Mixture 5 :
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp=
𝛒𝐦𝐢𝐱
0.499 × 32 + 0.5005× 46
= 0.7990
16.26+23.06
=
0.7990

= 48.7997 ml
Mixture 6:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp=
𝛒𝐦𝐢𝐱
0.6 × 32 + 0.40 × 46
=
0.7986
19.25+18.4
=
0.7986

= 47.0824 ml
Mixture 7:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp= 𝛒𝐦𝐢𝐱
0.71 × 32 + 0.298 × 46
= 0.7976
36.32
=
0.7976

= 45.2708 ml
Mixture 8 :
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp= 𝛒𝐦𝐢𝐱
0.8 × 32 + 0.2 × 46
= 0.7972
34.81
=
0.7972

= 43.6528ml
Mixture 9:
𝐗𝟏𝐌𝟏 + 𝐗𝟐𝐌𝟐
Vm exp= 𝛒𝐦𝐢𝐱
0.9 × 32 + 0.1 × 46
=
0.7953
33.46
= = 41.9967ml
0.7953

36 | P a g e
Table no. 2.3: Mole fraction vs Experimental molar volume

Mole fraction of methanol Experimental molar volume

0.1 55.549

0.2 53.865

0.3 52.2325

0.4 50.490

0.5 48.7997

0.6 47.0824

0.7 45.2708

0.8 43.6528

0.9 41.9967

Graph

60
Experimental molar volume

50

40

30 y = -16.999x + 57.265
R² = 0.9999
20

10

0
0 0.2 0.4 0.6 0.8 1
mole fraction of methanol

Graph 2.3: experimental molar volume(ml) vs mole fraction of methanol

37 | P a g e
This graph already demonstrates curve fitting with a linear trend. Here's the
breakdown:

1. Equation of the Fit: The equation provided on the graph is

Y = −16.999x+57.265

where:

o y is the experimental molar volume.

o X is the mole fraction of methanol.
2. Goodness of Fit (R²): The R2 value is 0.9999, which indicates an excellent fit.
This means that 99.99% of the variation in the experimental molar volume is
explained by the linear model.

Interpretation:

• Slope (−16.999):

The slope is negative, meaning that as the mole fraction of methanol increases,
the molar volume decreases. This suggests that methanol has a significant
impact on reducing the molar volume of the mixture.

• Y-Intercept (57.265):

When the mole fraction of methanol is zero (i.e., no methanol present), the molar
volume is approximately 57.265 units. This value corresponds to the molar
volume of the other component in the absence of methanol.

• Physical Meaning:

This relationship likely reflects a dilution or mixing effect where methanol

contributes to a reduction in the overall molar volume of the system. This could be
due to specific interactions between methanol molecules and the other
component(s) in the mixture.

38 | P a g e
Theoretical Molar volumes:
Molar mass of pure methanol
𝑉𝑚1 =
denisty of methanol

32
𝑉𝑚1 = = 40.506 ml
0.79
For Pure ethanol :
ρ = m / Vm
Molar mass of pure ethanol
Where’s 𝑉𝑚2 =
density of ethanol
46
𝑉𝑚2 = = 58.606ml
1.26

Mixture 1 ;
Vmther = X1V1 + X2V2
= 0.1 (40.506) + 0.9 (58.606)
= 56.8 ml
Mixture 2 ;
Vm ther = X1V1 + X2V2
= 0.2 (40.506) + 0.8 (58.606)
= 55.02ml
Mixture 3 ;
Vm ther = X1V1 + X2V2
= 0.3 (40.506) + 0.7 (58.606)
= 53.2282 ml
Mixture 4 ;
Vm ther = X1V1 + X2V2
= 0.4 (40.506) + 0.6 (58.606)
= 51.4356 ml
Mixture 5 ;
Vm ther = X1V1 + X2V2
= 0.5 (40.506) + 0.5 (58.606)
= 49.643ml
Mixture 6 ;
Vm ther = X1V1 + X2V2
= 0.6 (40.506) + 0.4 (58.606)

39 | P a g e
 = 47.8504 ml
Mixture 7 ;
Vm ther = X1V1 + X2V2
= 0.7 (40.506) + 0.3 (58.606)
= 46.0578 ml
Mixture 8 ;
Vm ther = X1V1 + X2V2
= 0.8 (40.506) + 0.2 (58.606)
= 44.2652 ml
Mixture 9 ;
Vm ther = X1V1 + X2V2
= 0.9 (40.506) + 0.1 (58.606)
= 42.472 ml

Table no. 2.4: Mole fraction of methanol vs Theoretical molar volume (ml)

Mole fraction of methanol Theoretical Molar Volume (ml)

0.1 56.8

0.2 55.02

0.3 53.2282

0.4 51.4356

0.5 49.643

0.6 47.8504

0.7 46.0578

0.8 44.2652

0.9 42.4726

40 | P a g e
Graph
Theoretica; molar volume (ml) 60
50
40
30 y = -17.917x + 58.6
R² = 1
20
10
0
0 0.2 0.4 0.6 0.8 1
Mole fraction of methanol
Graph 2.4:Theoretical Molar Vol (ml) vs mole fraction of methanol

1. Equation of the Fit: The equation provided on the graph is:

Y = − 17.917x+58.6

Where:

o y is the theoretical molar volume (in mL).

o x is the mole fraction of methanol.
2. Goodness of Fit (R²): The R2 value is exactly 1, which means the data
perfectly follows the linear model. This suggests the theoretical calculations
align perfectly with the expected trend.

Interpretation:

• Slope (−17.917): The slope is negative, indicating a linear decrease in the

molar volume as the mole fraction of methanol increases. Methanol reduces
the molar volume at a rate of 17.917mL per unit increase in mole fraction.
• Y-Intercept (58.6): When the mole fraction of methanol is zero (i.e., no
methanol present), the theoretical molar volume is 58.6mL. This represents the
molar volume of the other pure component in the system.
• Physical Significance: The graph indicates a theoretical prediction of molar
volume behavior when methanol is mixed with another component. The
perfect linearity (R² = 1) implies the theoretical model accurately represents
the system under study.

41 | P a g e
Comparison with Experimental Graph:

When compared to the experimental graph:

1. The slopes are slightly different (−16.999 for the experimental vs −17.917 for
the theoretical). This might indicate minor deviations due to real-world
experimental conditions, such as measurement inaccuracies or intermolecular
interactions not accounted for in the theoretical model.
2. The intercepts are also close (57.265 experimental vs 58.6 theoretical),
showing reasonable agreement

Excess Molar volumes

Mixture 1 ;
VmE = Vm exp - Vm ther
= 55.549- 56.8
= - 1.251ml
Mixture 2 ;
VmE = Vm exp - Vm ther
= 53.865- 55.02
= - 1.155ml
Mixture 3 ;
VmE = Vm exp - Vm ther
= 52.2325 – 53.2282
= -0.9957ml
Mixture 4 ;
VmE = Vm exp - Vm ther
= 50.490 – 51.4356
= -0. 9456ml
Mixture 5 ;
VmE = Vm exp - Vm ther
= 48.7997- 49.643
= -0. 8433ml
Mixture 6 ;
VmE = Vm exp - Vm ther

42 | P a g e
 = 47.0824 – 47.8504
= -0.768 ml
Mixture 7 :
VmE = Vm exp - Vm ther
= 45.2708 – 46.05
= -0.787 ml
Mixture 8 ;
VmE = Vm exp - Vm ther
= 43.6528 – 44. 2652
= -0.6124 ml
Mixture 9 ;
VmE = Vm exp - Vm ther
= 41. 9967 – 44.4726
= 0.4759 ml
Table no 2.5: Mole fraction vs Excess volume
Mole fraction of methanol Excess volume (ml)

0.1 -1.251

0.2 -1.155

0.3 -0.9957

0.4 -0.9456

0.5 0.8433

0.6 -0.768

0.7 -0.787

0.8 -0.6124

0.9 -0.4759

43 | P a g e
Graph

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

-0.2

y = 0.8872x - 1.314
-0.4 R² = 0.9686
Excess volume (ml)

-0.6

-0.8

-1

-1.2

-1.4
Mole fraction of methanol

Graph 2.5: Excess volume (ml) vs mole fraction of methanol

1. Equation of the Fit: The equation provided on the graph is:

Y = 0.8872x−1.314

Where:

o Y is the excess volume (in mL).

o X is the mole fraction of methanol.
2. Goodness of Fit (R²):

The R2 value is 0.9686, which indicates that the linear model explains
approximately 96.86% of the variation in the excess volume. While it is a strong
fit, there might be slight deviations from the linear trend due to system non-
idealities.

44 | P a g e
Interpretation:

• Slope (0.8872):

The positive slope suggests that the excess volume increases as the mole fraction of
methanol increases. This indicates a non-ideal mixing behavior where the addition of
methanol contributes to an increase in the excess volume.

• Y-Intercept (−1.314-1.314):

When the mole fraction of methanol is zero (pure other component), the excess
volume is negative at −1.314-1.314 mL. This could suggest that the system has a
contraction effect when the other component is pure.

• Physical Meaning:
o Excess Volume: Excess volume measures the deviation of the actual
volume from the ideal mixture volume. A positive value implies
expansion upon mixing, while a negative value implies contraction.
o In this case, the graph starts with a negative excess volume, indicating
contraction at lower methanol mole fractions. As methanol content
increases, the system trends toward positive excess volume, suggesting
expansion at higher methanol concentrations. This behavior could be
due to specific molecular interactions or differences in the molecular
sizes of the components.

Comparison to Other Graphs:

• The excess volume graph provides insight into the non-ideal behavior of the
system, complementing the experimental and theoretical molar volume graphs.
• The transition from contraction to expansion could indicate a significant
change in the intermolecular forces as methanol becomes the dominant
component.

45 | P a g e
Experiment no 3:
Determination of Liquid Viscosity of a Binary Mixture
Viscosity is one of the most important physical properties of liquids, reflecting their
internal resistance to flow under an applied force. In the study of binary liquid
mixtures, the determination of viscosity provides valuable insights into the molecular
interactions between the components of the mixture. When two liquids are mixed,
their viscosities do not necessarily follow a simple additive rule. This deviation from
ideal behavior can be attributed to intermolecular forces such as hydrogen bonding,
dipole-dipole interactions, and dispersion forces. Non-ideal behavior is often
characterized using terms like excess properties, which help quantify deviations from
ideality.
1. Theoretical Viscosity (ηid )

The ideal viscosity of a binary mixture assumes no specific interactions between the
components. It is calculated using:

ln ηid = ϕA ln ηA + ϕB ln ηB
Where:
• ηA, ηB are the Viscosities of pure components.
• ΦA , ϕB are the Volume fractions of components A and B.

2. Excess Viscosity (ηE)

Excess viscosity quantifies the deviation of the experimental viscosity from the ideal
viscosity:

ηE = ln ηexp − ln ηid
• Positive ηE : Indicates strong molecular interactions, such as hydrogen
bonding or dipole-dipole forces.
• Negative ηE : Suggests weaker interactions or steric hindrance.

Significance of Excess Viscosity

Excess viscosity is a measure of deviation from ideal behavior in liquid mixtures:

46 | P a g e
 1. Positive ηE : Indicates strong molecular interactions, such as hydrogen
bonding.
2. Negative ηE : Suggests weak interactions or steric hindrance.
It helps in:
• Characterizing molecular interactions.
• Optimizing formulations in industries like pharmaceuticals, lubricants, and
solvents.

3. Relative Viscosity (ηrel )

The relative viscosity is the ratio of the viscosity of the binary mixture to that of the
solvent:

𝜼 𝒎𝒊𝒙
𝜼 𝒓𝒆𝒍 =
𝜼 𝒔𝒐𝒍

4. Excess Molar Volume (VE):

VE = Vm,actual – Vm,ideal
• Vm,actual is the experimentally determined molar volume of the mixture.
• Vm,ideal is the molar volume calculated assuming the mixture behaves ideally
Vm,ideal = xAVA + xBVB
Here, xA and xB are the mole fractions, and VA and VB are the molar volumes of pure
components A and B.

Key Factors Behind the Decrease in Viscosity

1. Weaker Hydrogen Bonding:

o Ethanol molecules exhibit stronger hydrogen bonding compared to
methanol due to the larger alkyl group (−CH2CH3CH2CH3CH2CH3)
that enhances van der Waals interactions.
o When methanol is added, it disrupts the ethanol-ethanol hydrogen
bonding network, reducing the overall viscosity.
2. Lower Molecular Size and Weight:
o Methanol has a smaller molecular size and weight than ethanol, which
reduces intermolecular friction and leads to lower viscosity.

47 | P a g e
 3. Structural Effects:
o Methanol can fit into spaces between ethanol molecules, disrupting
their interactions and making the liquid less cohesive.
4. Non-Ideal Mixing Behavior:
o In non-ideal mixtures, the strength of methanol-ethanol interactions is
typically weaker than ethanol-ethanol interactions. This reduces the
overall viscosity compared to pure ethanol.
5. Entropy Increase:
o Mixing methanol and ethanol increases the entropy of the system,
which reduces the energy required for molecular motion and lowers the
viscosit

Significance of Excess Viscosity (ηE)

Excess viscosity (ηE) is an important parameter used to understand the non-ideal

behavior of liquid mixtures. It represents the deviation of the actual viscosity of a
mixture from the viscosity expected for an ideal mixture. Mathematically, it is defined
as:
ηE =ηactual - ηideal
Here, ηactual is the experimentally measured viscosity of the mixture, and η ideal is the
viscosity calculated using a linear combination of the pure components' viscosities
based on their mole fractions.

1. Understanding Molecular Interactions

• Positive ηE:
o Indicates strong attractive forces between molecules.
o These interactions may include hydrogen bonding, dipole-dipole
interactions, or specific associations between molecules.
o Results in increased resistance to flow, as molecules form networks or
clusters.
o Example: Water-ethanol mixtures show positive excess viscosity due
to hydrogen bonding.

• Negative ηE:

48 | P a g e
 o Suggests weak intermolecular forces or repulsive interactions
between molecules.
o Molecules may be structurally incompatible, leading to reduced
resistance to flow.
o Example: Benzene-carbon tetrachloride mixtures exhibit negative
excess viscosity due to molecular incompatibility.

2. Analyzing Mixture Behavior

Excess viscosity provides insights into the behavior of real mixtures compared to
ideal mixtures:

• Ideal Mixtures: Viscosity is a simple additive property, and ηE =0.

• Non-Ideal Mixtures:

o Deviations occur due to molecular size, shape, and interactions.

o Helps identify whether the mixture has synergistic effects (positive
deviation) or destabilizing effects (negative deviation).

3. Industrial Applications

a. Process Optimization:

• Flow Behavior: Excess viscosity helps in designing pipelines, reactors, and

transport systems by predicting flow behavior under various conditions.

• Separation Processes: Used to analyze phase behavior and optimize

processes like distillation, extraction, and membrane separation.

b. Lubricant and Fluid Design:

• Customized Fluids: Helps design lubricants with specific viscosities by

analyzing how components interact and affect flow resistance.

• Energy Efficiency: Excess viscosity helps in selecting or modifying fluids to

reduce energy losses due to friction.

c. Food and Beverage Industry:

49 | P a g e
 • Texture and Stability: Ensures desired viscosity for stable emulsions, sauces,
or beverages by analyzing how ingredients interact volumetrically.

d. Pharmaceuticals and Healthcare:

• Drug Formulations: Excess viscosity data is used to develop liquid

formulations with the right flow properties for delivery systems like syrups,
injectables, or topical gels.

4. Thermodynamic and Structural Insights

Excess viscosity is closely linked to the thermodynamic and structural properties of

mixtures:

• Energy Changes:

o Positive ηE indicates energy dissipation due to strong molecular

associations.
o Negative ηE suggests minimal energy loss due to weak or repulsive
interactions.

• Structural Effects:

o Highlights the role of molecular size, shape, and orientation in

influencing flow properties.
o For example, long-chain molecules like polymers often exhibit positive
ηE due to entanglement effects.

5. Environmental and Sustainability Applications

• Eco-Friendly Solvent Design:

o Excess viscosity helps evaluate the performance of green solvents and

their mixtures for sustainable processes.

• Minimizing Energy Use:

Data on ηE can optimize flow conditions in industrial processes, reducing energy

consumption.

50 | P a g e
Objective :

To measure the viscosity of binary liquid mixtures at different compositions and

calculate the excess viscosity (ηE), theoretical viscosity (ηid), and relative viscosity
(ηrel ).

Apparatus and Materials

• Ostwald Viscometer: Used to determine the time of flow for liquids.

• Stopwatch: To measure the flow time.
• Thermostatic Bath: Maintains a constant temperature throughout the
experiment.
• Volumetric Flasks and Pipettes: For preparing accurate mixtures of binary
liquids.
• Methanol, Ethanol, Distilled Water: The liquids used for the binary mixtures.
• Density Bottle: To measure the density of the binary mixture.

Procedure

Step 1: Preparation of Binary Mixtures

1. Prepare a series of binary mixtures (e.g., methanol and ethanol) by varying the
volume fractions (ϕ) of each component. Use precise measurements to ensure
accuracy.
2. Record the volume fractions for all prepared mixtures. Example:
a. Methanol: 53%
b. Ethanol: 26%
c. Distilled Water: 21% (Adjust these ratios for each set of mixtures.)

Step 2: Calibration of Viscometer

1. Wash and dry the viscometer thoroughly to ensure no contamination.
2. Calibrate the viscometer using distilled water at the desired temperature (e.g.,
25°C).
3. Record the flow time (t) for distilled water to calculate the viscometer constant
(k ) using the formula:

51 | P a g e
 𝑣
k=
𝑡

Step 3: Measurement of Flow Time

1. Fill the viscometer with the binary mixture, ensuring it reaches the required
level.
2. Place the viscometer in a thermostatic bath set to the desired temperature.
Allow sufficient time for the mixture to reach thermal equilibrium.
3. Measure the time (t) taken for the liquid to flow between the upper and lower
marks on the viscometer using a stopwatch. Perform the measurement in
triplicate for accuracy.

Step 4: Data Collection and Calculations

1. For each mixture, note the flow time (t ) and calculate the kinematic viscosity
(ν ):
ν=k⋅t
2. Measure the density (ρ ) of each binary mixture using a density bottle.
3. Calculate the dynamic viscosity (η ):
η=ρ⋅ν

Step 5: Repeat for All Mixtures

1. Repeat the process for all prepared binary mixtures.

2. If required, conduct the experiment at multiple temperatures to study the effect
of temperature on viscosity.

Calculation :
I. Viscosity
For pure methanol :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.789 × 68.8
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.23 mPa. s

52 | P a g e
For pure ethanol :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = 𝛒𝐰 ×𝐭𝐰
×ɳw
0.792 × 49
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 0.936 mPa. s

Mixture 1 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.793 × 76
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.453 mPa. s

Mixture 2 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰
0.798 × 70
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.358 mPa.s

Mixture 3 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰
0.803 × 69
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.34 mPa. s

Mixture 4 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.808 × 69
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.32 mPa. s

53 | P a g e
Mixture 5 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = 𝛒𝐰 ×𝐭𝐰
×ɳw
0.813× 66
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.29 mPa. s

Mixture 6 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.818 × 63.5
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.25 mPa. s

Mixture 7 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰
0.836 × 60.5
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.20 mPa. s

Mixture 8 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.828 × 54
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 1.10 mPa. s

Mixture 9 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.834× 44.06
viscosity ɳ = × 1.14
0.9991 × 47.3

viscosity ɳ = 0.90 mPa. s

54 | P a g e
II. Ideal Viscosity :
Mixture 1 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.1 (ln 0.56) + 0. 9 (ln 1.47)
ln ɳid = 0.1 (-0.43) + 0.9 (0.38)
ɳid = ln-1 1.355
ɳid = 1.280 mPa. s
Mixture 2 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0. 2 (ln 0.56) + 0.8 (ln 1.47)
ln ɳid = 0.2 (-0.43) + 0.8 (0.38)
ɳid = ln-1 1.249
ɳid = 0.2221 mPa. s
Mixture 3 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.3 (ln 0.56) + 0.7 (ln 1.47)
ln ɳid = 0.3 (-0.43) + 0.7 (0.38)
ɳid = ln-1 1.151
ɳid = 0.1404 mPa. s
Mixture 4 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.4 (ln 0.56) + 0.6 (ln 1.47)
ln ɳid = 0.4 (-0.43) + 0.6 (0.38)
ɳid = ln-1 1.061
ɳid = 0.0588 mPa. s
Mixture 5 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.5 (ln 0.56) + 0.5 (ln 1.47)
ln ɳid = 0.5 (-0.43) + 0.5 (0.38)
ɳid = ln-1 0.977
ɳid = -0.0228 mPa. s
Mixture 6 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)

55 | P a g e
 ln ɳid = 0.6 (ln 0.56) + 0.5 (ln 1.47)
ln ɳid = 0.6 (-0.43) + 0.5 (0.38)
ɳid = ln-1 0.787
ɳid = -0.104 mPa. s
Mixture 7 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.7 (ln 0.56) + 0.3 (ln 1.47)
ln ɳid = 0.7 (-0.43) + 0.3 (0.38)
ɳid = ln-1 0.653
ɳid = -0.185 mPa. s
Mixture 8 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.8 (ln 0.56) + 0.2 (ln 1.47)
ln ɳid = 0.8 (-0.43) + 0.2 (0.38)
ɳid = ln-1 0.537
ɳid = -0.27 mPa. s
Mixture 9 :
ln ɳid = Φ1ln(ɳ1) + Φ2ln(ɳ2)
ln ɳid = 0.9 (ln 0.56) + 0.1 (ln 1.47)
ln ɳid = 0.9 (-0.43) + 0.1 (0.38)
ɳid = ln-1 0.447
ɳid = -0.349 mPa. s

III. Experimental Viscosity :

Mixture 1 :
𝛒𝐬 × 𝐓𝐬
ɳexp =
𝛒𝐰 ×𝐭𝐰
0.793 × 76
ɳexp =
0.9991 × 47.3
ɳ exp
= 1.27 mPa. s
Mixture 2 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰

0.798 × 70
ɳexp =
0.9991 × 47.3
ɳexp = 1.18 mPa. s

56 | P a g e
Mixture 3 :
𝛒𝐬 × 𝐓𝐬
ɳexp =
𝛒𝐰 ×𝐭𝐰
0.803 × 69
ɳexp =
0.9991 × 47.3
ɳexp = 1.17 mPa. s
Mixture 4 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰
0.808 × 69
ɳexp =
0.9991 × 47.3
ɳexp
= 1.162 mPa. s
Mixture 5 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰
0.813 × 66
ɳexp =
0.9991 × 47.3
ɳexp = 1.135 mPa. s
Mixture 6 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰
0.818 × 63.5
ɳexp =
0.9991 × 47.3
ɳexp = 1.099 mPa. s
Mixture 7 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰

0.826× 60.5
ɳexp =
0.9991 × 47.3
ɳexp
= 1.057 mPa. s
Mixture 8 :
𝛒𝐬 × 𝐓𝐬
ɳexp = 𝛒𝐰 ×𝐭𝐰
0.828 × 54
ɳexp =
0.9991 × 47.3
ɳexp = 0.946 mPa. s
Mixture 9 :
𝛒𝐬 × 𝐓𝐬
ɳexp =
𝛒𝐰 ×𝐭𝐰
0.834 × 44.06
ɳexp =
0.9991 × 47.3

57 | P a g e
 ɳexp = 0.7775 mPa. s
IV. Difference in Viscosity :
Mixture 1:
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = 0.239 －1.28
Δlnɳexp = -1.04
Mixture 2 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = 0.165 －0.2221
Δlnɳexp = -0.0571
Mixture 3 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp =0.157 －0.1404
Δlnɳexp = 0.0166

Mixture 4 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = 0.15 － 0.0588
Δlnɳexp = 0.0912

Mixture 5 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = 0.1266 － (-0.02288)
Δlnɳexp = 0.1494
Mixture 6 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = 0.094 － (-0.104)
Δlnɳexp = 0.198
Mixture 7 :
Δln = ln ɳexp － ln ɳid
Δlnɳexp = 0.554 － (-0.185)
Δlnɳexp = 0.739

58 | P a g e
 Mixture 8 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = -0.0555 －(-0.27)
Δlnɳexp = 0.2145
Mixture 9 :
Δlnɳexp = ln ɳexp － ln ɳid
Δlnɳexp = -0.2516 －(-0.349)
Δlnɳexp = 0.0974
Observations :
Table no 3.1: Experimental viscosity vs mole fraction

Experimental viscosity Mole fraction

0.1 1.453
0.2 1.358
0.3 1.34
0.4 1.32
0.5 1.29
0.6 1.25
0.7 1.20
0.8 1.10
0.9 0.9

Graphs :
1.5

1.4

1.3

1.2

viscosity ɳ 1.1

1 y = -0.7751x4 - 1.3842x3 + 2.639x2 - 1.423x + 1.565

R² = 0.9966
0.9

0.8
0 0.2 0.4 0.6 0.8 1
mole fraction of MeOH
59 | P a g e Graph 3.1: Experimental viscosity vs mlole fracion of methanol
Equation fitting:
The equation of the graph is:
Y= 0.7751x4 – 1.3842x3 + 2.639x2 – 1.423x + 1.565
Here is a step-by-step explanation of what it represents:
General Form:
This is a fourth-degree polynomial equation (quartic equation), where:
⚫ y represents the experimental viscosity (dependent variable).
⚫ x represents the mole fraction of methanol (MeOH) (independent variable).
⚫ The terms x4,x3,x2,x and the constant 1.565 describe how viscosity depends
on the mole fraction of methanol.
Components of the Equation:
1. 0.7751x4: This is the quartic term. Its influence grows as becomes significant at
higher mole fractions, contributing to the overall curve shape.
2. -1.3842x3: The cubic term adds complexity to the curve, allowing it to capture
changes in slope as the mole fraction changes.
3. 2.639x2: The quadratic term contributes to the curvature, representing how
viscosity initially changes as the mole fraction increases.
4. -1.423x: The linear term shows how viscosity decreases proportionally to the
mole fraction in certain regions.
5. 1.565: This is the constant (intercept), which represents the viscosity when
(pure solvent without methanol).
Behavior of the Curve:
The equation models the relationship between the mole fraction of methanol (x) and
the viscosity (y):
• At x=0, the viscosity starts at approximately (pure solvent).
• As x increases, the viscosity decreases non-linearly, with the
contributions of all terms determining the overall curve shape.
• The fourth-degree polynomial enables the curve to match the
experimental data points accurately.
𝑅2 = 0.9966:
The value shows that the polynomial equation provides an excellent fit to the
experimental data, explaining 99.66% of the variation in viscosity based on the mole
fraction.

60 | P a g e
Purpose of the Equation :
This equation allows:
1. Prediction of viscosity for any given mole fraction of methanol within the
tested range.
2. Analysis of how viscosity behaves as methanol is added to the solvent,
which is important in understanding mixture properties.

Graph Interpretation

The graph of viscosity versus the mole fraction of methanol shows a decreasing
trend due to:

• The lower intrinsic viscosity of methanol.

• Weaker intermolecular interactions as methanol concentration increases.
• Disruption of ethanol’s hydrogen bonding network

If the viscosity of the methanol-ethanol mixture increases with the mole fraction of
methanol, it indicates a different interaction dynamic between the two components.
This behavior, while less common, can occur due to specific intermolecular effects or
structural arrangements in the mixture. Here's how to interpret an increase in
viscosity
Table no 3.2: Ideal viscosity vs Moles fraction

Ideal viscosity Moles fraction

0.1 1.355

0.2 1.249

0.3 1.151

0.4 1.061

0.5 0.977

0.6 0.787

0.7 0.653

0.8 0.537

0.9 0.447

61 | P a g e
Graph

Ideal viscosity vs Moles fraction of methanol

1.6

1.4

1.2
y = -1.173x + 1.4995
R² = 0.9912
1
viscosity ɳ

0.8

0.6

0.4

0.2

0
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1
moles of MeOH

Graph 3.2 Ideal viscosity vs mole fraction of methanol

Graph explanation:
The graph provided for the "Ideal viscosity vs Mole fraction of methanol" has the
following equation:
Y = −1.173x+1.4995
with R2 = 0.9912
Interpretation:
1. Linear Relationship:
o Unlike the experimental viscosity graph, this graph exhibits a linear
relationship between the ideal viscosity (η) and the mole fraction of
methanol (x).
o The linear equation suggests that the ideal viscosity decreases at a
constant rate as the mole fraction of methanol increases.
2. Slope and Intercept:
o The slope of the line (−1.173) indicates that for every unit increase in
the mole fraction of methanol, the viscosity decreases by
approximately 1.173 units (in the chosen viscosity scale).

62 | P a g e
 o The y-intercept (1.4995) represents the viscosity when the mole
fraction of methanol is zero (i.e., pure solvent).
3. Quality of Fit (R2=0.9912R^2 = 0.9912):
o The R2 value of 0.9912 indicates a very strong linear relationship. The
model explains 99.12% of the variation in the data.
4. Comparison with Experimental Data:
o In comparison to the experimental viscosity graph (nonlinear), the
ideal viscosity decreases more uniformly with methanol concentration.
o The deviation of experimental data from ideal behavior may be
attributed to non-ideal interactions in the methanol-water mixture, such
as hydrogen bonding or structural effects.
5. Practical Implications:
o This graph is crucial for determining deviations from ideal mixing
behavior in solutions.
o It can be used to predict the ideal viscosity of the mixture for
theoretical studies or as a reference for analyzing experimental
deviations.
Table no 3.3 : Δln exp vs moles fraction of methanol

Δln exp moles fraction of methanol

0.1 -1.04

0.2 -0.0571

0.3 0.0166

0.4 0.0912

0.5 0.1494

0.6 0.198

0.7 0.739

0.8 0.2145

0.9 0.0974

63 | P a g e
Graph

1
0.8 y = 173.49x5 - 490.6x4 + 514.91x3 - 248.22x2 + 55.296x - 4.5617
0.6 R² = 0.9317
0.4
0.2
Δlnɳexp

0
-0.2 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1

-0.4
-0.6
-0.8
-1
-1.2
Mole fraction of methanol

Graph 3.3: Δlnɳexp vs moles fraction of methanol

The provided graph, Δln η vs Mole fraction of methanol includes a fitted equation and
the corresponding R2 value:
y=173.49x5−490.6x4+514.91x3−248.22x2+55.296x−4.5617
with R2 = 0.9317
Interpretation:
1. Behavior of Δln ηexp
o Δln ηexp represents the deviation in the natural logarithm of viscosity
from its ideal value. It provides a measure of the non-ideal mixing
behavior of the methanol-water system.
o The graph shows a nonlinear trend with peaks and valleys, indicating
significant non-ideal interactions between methanol and water
molecules.
2. Mathematical Fit:
o A fifth-degree polynomial has been used to fit the data. The higher-
order terms suggest complex dependencies of Δln ηexp on the mole
fraction of methanol.
o The curve highlights regions where molecular interactions are more
pronounced (e.g., around x=0.7x = 0.7, where Δln ηexp peaks).
3. Quality of Fit (R2=0.9317):
o An R2 value of 0.9317 indicates a reasonably good fit. However, it is
slightly lower than the fits of previous graphs, suggesting some

64 | P a g e
 variability in the data that might not be fully captured by the
polynomial.
4. Physical Explanation:
o Peaks in Δlnηexp suggest enhanced interactions, such as hydrogen
bonding or structural ordering, between methanol and water molecules
at specific concentrations.
o The valleys indicate reduced interaction or the dominance of one
component’s properties over the mixture.
5. Practical Implications:
o This graph is crucial for understanding the thermodynamic and
structural behavior of methanol-water mixtures.
o It can help in optimizing mixture compositions for processes where
specific viscosity deviations are desirable or problematic.

Key Features of the Alternating Theoretical Viscosity Pattern

1. Alternating Peaks and Troughs:

o Peaks: Indicate compositions where intermolecular interactions (e.g.,
hydrogen bonding) or structural organization are at their strongest.
o Troughs: Indicate weaker interactions, better molecular packing, or
less cohesive structures.
2. Non-Ideal Mixing:
o The alternating pattern reflects non-ideal mixing behavior, where the
interactions between methanol and ethanol molecules vary non-linearly
with composition.

Causes of the Alternating Theoretical Viscosity Pattern:

1. Hydrogen Bonding Dynamics:

Varying dominance of methanol-methanol, ethanol-ethanol, and methanol-

ethanol hydrogen bonding at different mole fractions.

2. Structural Effects: Formation and breakdown of transient clusters or

microstructures due to optimal hydrogen bonding.

65 | P a g e
 3. Packing Efficiency:

Size differences between methanol and ethanol lead to alternating efficient and
inefficient molecular packing.

4. Thermodynamic Contributions:

Non-linear changes in enthalpy and entropy of mixing alter interaction strength

and cohesion.

5. Non-Ideal Mixing Behavior:

Non-linear variation in interaction strengths between methanol and ethanol

molecules with composition.

Interpretation of the Graph

• Peaks (Higher Viscosity):

o Strong methanol-ethanol interactions or clustering dominate.
o Indicates greater intermolecular cohesion and resistance to flow.
• Troughs (Lower Viscosity):
o Weaker interactions or better packing dominate.
o Suggests less resistance to flow and reduced hydrogen bonding.

Discussion :
The viscosity of binary mixtures (methanol and ethanol) was measured at different
compositions to investigate molecular interactions. The experimental viscosity
showed a non-linear relationship with the mole fraction of methanol due to variations
in molecular interactions, hydrogen bonding, and packing efficiency.
Strong molecular interactions resulted in increased viscosity at certain mole fractions,
while weaker interactions led to lower viscosity. The ideal viscosity calculation
deviated from experimental results, indicating non-ideal mixing behavior.
Excess viscosity calculations confirmed that methanol disrupted ethanol's hydrogen
bonding network, reducing overall molecular cohesion at higher mole fractions of
methanol.
____________________________________________________________________

66 | P a g e
Experiment no 4
Measure densities of different salt ions.
Introduction

Salt ions are categorized as either structure makers or structure breakers based on
their effect on the hydrogen-bonded network of water. Understanding these effects is
crucial in chemistry, biology, and environmental science, as they influence solubility,
viscosity, density, and many biochemical reactions.

▪ Structure Makers:

Enhance the water structure by promoting hydrogen bonding.

▪ Structure breaker:

Disrupt hydrogen bonding, leading to increased randomness in water structure.

This experiment aims to measure the density of solutions of salts classified as

structure breakers and makers. By studying the relationship between salt
concentration and solution density, we can better understand the interactions between
ions and the water network.

Hydrogen Bonding in Water

Water molecules are extensively hydrogen-bonded, creating a structured network. The

introduction of ions into water can either:

• Strengthen the network (structure makers), or

• Weaken the network (structure breakers).

Ions as Structure Makers

Structure-making ions are typically small and highly charged, like:

• Mg2+, Al3+, SO42−. These ions strongly attract water molecules, leading to:

• Increased local ordering around the ion.

• A denser solution due to tightly bound hydration shells

67 | P a g e
Ions as Structure Breakers

Structure-breaking ions are larger or have lower charge densities, such as:

• K+, Cl−, Br−. These ions:

• Interact weakly with water molecules.
• Disrupt the hydrogen-bonded network, increasing randomness and sometimes
reducing density.

Density of Solutions

The density ρ of a salt solution is influenced by:

1. Concentration of the Salt: Higher concentrations generally increase density.

2. Ion Hydration: The extent to which ions interact with water molecules.

The density of the solution is given by:

𝑚
𝜌=
𝑉

Significance of Solvation Studies

Structure-breaking and structure-making ions affect the folding and stability of

proteins by interacting with the hydration layers around biomolecules. For instance:
Structure breakers can destabilize protein structures. Structure makers stabilize
proteins by reinforcing hydration shells.

The activity of enzymes depends on their interactions with surrounding water

molecules, which can be altered by the presence of specific ions.

In short, solvation studies help us understand how ions interact with water and affect
important processes like protein folding and enzyme activity.By studying structure
makers and breakers, we gain valuable insights into how molecules behave in
different environments.
This knowledge has real-world applications in medicine, environmental science, and
technology, making it a key area of research with the potential to solve everyday
problems and improve lives.

68 | P a g e
Objective :

The objective of this experiment is to measure and compare the densities of solutions
containing different salt ions to understand how ionic composition and concentration
influence solution density. This helps in applications like analyzing seawater salinity
and validating theoretical models of ionic behavior.

Materials

• Analytical balance
• Pycnometer or density bottle
• Measuring cylinder
• Deionized water
• Salt samples
• Thermometer
• Distilled water

Procedure:

⚫ Preparation of Salt Solutions

1. Weigh a specific mass of each salt to prepare solutions of varying

concentrations (e.g., 0.1 M,0.5 M,1.0 M.
2. Dissolve the salt in deionized water using a volumetric flask to ensure
accuracy.
3. Mix thoroughly to ensure complete dissolution.

⚫ Density Measurement

1. Calibrate the Density Bottle:

a. Weigh the empty, clean, and dry bottle.
b. Fill it with distilled water and weigh it again to determine its volume.
2. Measure the Density of Solutions:
a. Fill the density bottle with the salt solution, ensuring no air bubbles.
b. Weigh the filled bottle.

69 | P a g e
 c. Calculate the density using the equation.
3. Repeat for All Solutions:
a. Conduct the procedure for all salt types and concentrations.
b. Record temperature to account for temperature dependence.
Calculation :
I. Densities :
For Solution 0.01 :
Mass of empty bottle (m1) = 10.05 g
35.41+ 35.59+35.63
Mass of empty bottle + sol (m2)=
3
m2= 35.54 g
Mass of sol = m2－m1 = 35.54 g － 10.05 g = 25.49 g
Now , ρ = mass/ Vc :
25.49 𝑔
ρ=
26.16 𝑚𝑙
ρ = 0 .947 g ml-1
For Solution 0.02 :
Mass of empty bottle (m1) = 10.05 g
37.56+ 37.75+37.74
Mass of empty bottle + sol (m2)=
3
m2 = 35.75 g
Mass of sol = m2－m1 = 35.75 g － 10.05 g = 25.7 g
Now , ρ = m / Vc :
25.7 𝑔
ρ=
26.16 𝑚𝑙
ρ = 0.982 g ml-1
For Solution 0.04 :
Mass of empty bottle (m1) = 10.05 g
36.00+36.01 +36.02
Mass of empty bottle + sol (m2)=
3
m2 = 36.01 g
Mass of sol = m2－m1 = 36.01 g － 10.05 g = 25.96 g
Now , ρ = m / Vc :
25.96 𝑔
ρ=
26.16 𝑚𝑙
ρ = 0.9929 g ml-1

70 | P a g e
For Solution 0.08 :
Mass of empty bottle (m1) = 10.05 g
37.73+ 37.28+37.21
Mass of empty bottle + sol (m2)=
3
m2 = 37.40 g
Mass of sol = m2－m1 = 37.40 g － 10.05 g = 27.35 g
Now , ρ = m / Vc :
27.35 𝑔
ρ=
26.16 𝑚𝑙
ρ = 1.04 g ml-1

For Solution 0.12 :

Mass of empty bottle (m1) = 10.05 g
37.87+ 37.86+37.79
Mass of empty bottle + sol (m2)=
3
m2 = 37.84 g
Mass of sol = m2－m1 = 37.84 g － 10.05 g =27.79 g
Now , ρ = m / Vc :
27.79 𝑔
ρ=
26.16 𝑚𝑙
ρ = 1.06 gml-1
For Solution 0.16 :
Mass of empty bottle (m1) = 10.05 g
38.64+ 38.64+38.55
Mass of empty bottle + sol (m2)=
3
m2 = 38.61 g
Mass of sol = m2－m1 = 38.61 g － 10.05 g = 28.56 g
Now , ρ = m / Vc :
28.56 𝑔
ρ=
26.16 𝑚𝑙
ρ = 1.09 g ml-1
For Solution 0.20 :
Mass of empty bottle (m1) = 10.05 g
39.42+39.25 +39.23
Mass of empty bottle + soln(m2)=
3
m2 =39.3 g

71 | P a g e
 Mass of sol = m2－m1 = 39.3 g － 10.05 g = 29.95 g
Now , ρ = m / Vc :
29.95 𝑔
ρ=
26.16 𝑚𝑙
ρ = 1.12 g ml-1
For Solution 0.24 :
Mass of empty bottle (m1) = 10.05 g
39.59+39.51 +39.53
Mass of empty bottle + sol (m2)=
3
m2 = 39.54 g
Mass of sol = m2－m1 = 39.54 g － 10.05 g = 29.49 g
Now , ρ = m / Vc :
29.49 𝑔
ρ=
26.16 𝑚𝑙
ρ = 1.27 gml-1
II. Viscosity
For Solution 0.01 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.974 ×52.96
viscosity ɳ = × 1.14
0.9991 × 58.64
viscosity ɳ = 1.0037
For Solution 0.02 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.982 ×55.47
viscosity ɳ = × 1.1
0.9991 × 58.64
viscosity ɳ = 1.060
For Solution 0.04 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

0.992 ×52.41
viscosity ɳ = × 1.14
0.9991 × 58.64
viscosity ɳ = 1.012
For Solution 0.08 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰
1.04×53.88
viscosity ɳ = × 1.14
0.9991 × 58.64

72 | P a g e
 viscosity ɳ = 1.09
For Solution 0.12:
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = 𝛒𝐰 ×𝐭𝐰
×ɳw
1.06 ×51.65
viscosity ɳ = × 1.14
0.9991 × 58.64
viscosity ɳ = 1.065
For Solution 0.16 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

1.09 × 51.41
viscosity ɳ = × 1.14
0.9991 × 58.64
viscosity ɳ = 1.090
For Solution 0.20 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰
1.12 × 52.35
viscosity ɳ = × 1.14
0.9991 × 58.64
viscosity ɳ = 1.14
For Solution 0.24 :
𝛒𝐋 × 𝐓𝐋
viscosity ɳ = ×ɳw
𝛒𝐰 ×𝐭𝐰

1.27 ×50.37
viscosity ɳ = × 1.14
0.9991 × 58.64
Viscosity ɳ = 1.24

Table no 4.1: Solution percentage vs Denisty

Solution percentage Density (g/ml)

0.01 0.974
0.02 0.982
0.04 0.992
0.08 1.04
0.12 1.06
0.16 1.09
0.2 1.12
0.24 1.27

73 | P a g e
Graphs :

1.4

1.2

1
y = 4.4146x2 + 0.0144x + 0.9838
0.8
R² = 0.9443
Density 0.6

0.4

0.2

0
0 0.05 0.1 0.15 0.2 0.25 0.3
Solution percentage

Graph 4.1 : Solution percentage vs density (g/ml)

This graph represents the relationship between solution percentage (x-axis) and
density (y-axis), and the trend is described by the quadratic equation:
Y=4.4146x2 + 0.0144x + 0.9838
Here’s the explanation in simple terms:

1. Equation Components:

⚫ 4.4146x2: This is the quadratic term, meaning that as the solution percentage
increases, the effect on density grows faster (non-linear growth). It shows that
density doesn’t increase at a constant rate—it accelerates slightly with
increasing solution percentage.
⚫ 0.0144x: This is the linear term, which indicates a small consistent increase in
density as the solution percentage rises.
⚫ 0.9838: This is the y-intercept. It tells us the density value (approximately
0.9838) when the solution percentage is 0 (i.e., pure solvent or no solute
added).
2. Shape of the Curve:
Since the equation is quadratic, the graph forms a parabola. In this case, the parabola
opens upwards because the coefficient of x2 (4.4146) is positive. This suggests that as
the solution percentage increases, the density also increases, but not in a straight
line—it bends upward.

74 | P a g e
3. R² Value (Goodness of Fit):

⚫ The R² = 0.9443 shows how well the equation fits the data.

⚫ An R² close to 1 means the equation accurately describes the trend in the

graph. Here, 94.43% of the variation in density is explained by the solution
percentage using this equation.

4. Practical Meaning:

The graph shows how the density of a solution changes as you increase the
concentration of solute (solution percentage). Initially, there’s a slow increase, but at
higher solution percentages, the density rises more rapidly due to the quadratic
relationship.

When you measure the densities of KCl solutions of varying concentrations and plot
the density against the percentage solution, the graph typically shows an increase in
density as the concentration increases. Here's the interpretation of the graph:

1. Relationship Between Density and Solute Concentration

• Density increases with concentration because adding KCl to water increases

the mass of the solution without significantly increasing its volume.

• The increase in density reflects the number of dissolved ions (K⁺ and Cl⁻) in
the solution. A higher percentage of KCl means more ions are present, leading
to a denser solution.

2. Slope of the Graph

• The slope of the graph indicates the rate at which the density increases with
concentration.

o If the slope is steep, the density rises significantly with small changes
in concentration.

o A less steep slope suggests a more gradual increase in density

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Table no. 4.2: Solution percentage vs viscocity

Solution percentage Viscosity

0.01 1.0037

0.02 1.06

0.04 1.012

0.08 1.09

0.12 1.065

0.16 1.09

0.2 1.14

0.24 1.24

Graph

1.4

1.2

0.8
y = 3.9382x2 - 0.1573x + 1.0328
Viscosity R² = 0.8729
0.6

0.4

0.2

0
0 0.05 0.1 0.15 0.2 0.25 0.3

Solution percentage

Graph no. 4.2 : Solution percentage vs Viscosity

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The equation displayed on the graph is:
y = 3.9382x² - 0.1573x + 1.0328
Explanation:
y: This represents the viscosity of the solution. In other words, how resistant the
solution is to flow.
x: This represents the solution percentage, which likely indicates the concentration of
a solute (the substance being dissolved) in the solution.
Interpretation:
The graph shows a quadratic relationship between the solution percentage and the
viscosity. This means that as the solution percentage increases, the viscosity doesn't
change linearly. Instead, it increases at an accelerating rate.
The equation is a quadratic function, which is characterized by the x² term. This
indicates that the relationship between the solution percentage and viscosity is not a
simple straight line.
R² Value:
The R² value (0.8729) is a measure of how well the equation fits the data points on
the graph. A value closer to 1 indicates a stronger fit, meaning the equation is a good
predictor of the viscosity based on the solution percentage.
Inferences:
Increasing Concentration:
As the concentration of the solute increases (higher solution percentage), the
viscosity of the solution generally increases.
Non-linear Relationship:
The increase in viscosity is not proportional to the increase in solution percentage. It's
likely that at higher concentrations, the solute molecules interact more strongly with
each other and with the solvent molecules, leading to a more significant increase in
viscosity.

Possible Causes of Alternating Pattern

• Electrostatic Effects: Ions in solution can cause varying effects depending on

their concentrations. At certain concentrations, the electrostatic forces between
ions may either facilitate or hinder the flow of the solution.

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 • Hydration Effects: At different concentrations, the extent of hydration of the
ions and the structure of water molecules around the ions can change,
influencing the viscosity in alternating ways.
• Saturation Effects: Once the KCl solution nears its saturation point, there
may be less effective dissociation or ion hydration, which could cause the
viscosity to behave unpredictably or in a non-linear manner

The alternating pattern in the viscosity vs. KCl concentration graph suggests complex
interactions between the K⁺ and Cl⁻ ions and water molecules. At low concentrations,
viscosity increases due to ion hydration. At medium concentrations, ion-ion
interactions may reduce viscosity by facilitating water flow. At high concentrations,
viscosity rises again as ion interactions increase resistance. The alternating pattern
reflects these varying effects, where viscosity fluctuates based on ion concentration,
hydration, and water structure changes

Discussion :
The densities of salt solutions were measured to classify ions as structure-makers
(kosmotropes) or structure-breakers (chaotropes). Structure-makers increase the order
of water molecules around them, resulting in higher densities, whereas structure-
breakers disrupt water structure, reducing density. The findings highlight the impact
of ionic hydration and ion-water interactions on the density of
solutions.Understanding these properties is critical for applications in solution
chemistry and industrial processes.

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Refernces:
1. Batchelor, G. K. (2000). An Introduction to Fluid Dynamics. Cambridge
University Press.
2. Poling, B. E., Prausnitz, J. M., & O'Connell, J. P. (2001). The Properties of
Gases and Liquids.
3. McGraw-Hill. Vswanath, D. S., Natarajan, G. (1989). Data Book on the
Viscosity of Liquids. Hemisphere Publishing Corporation
4. Marcus, Y. (2009). Ions in Solution and Their Solvation. Wiley.
5. Israelachvili, J. N. (2011). Intermolecular and Surface Forces. Academic Press.
6. Helgeson, H. C., Kirkham, D. H., & Flowers, G. C. (1981). Theoretical
Prediction of the Thermodynamic Behavior of Aqueous Electrolytes at High
Pressures and Temperatures. American Journal of Science.
7. CRC Handbook of Chemistry and Physics, Density and Molar Volume Tables.
8. Reichardt, C. & Welton, T. (2010). Solvents and Solvent Effects in Organic
Chemistry. Wiley-VCH.
9. ASTM E542-20: Standard Practice for Calibration of Laboratory Volumetric
Apparatus.
10. Harris, D. C. (2015). Quantitative Chemical Analysis. W. H. Freeman and
Company.
11. ISO 4787:2010 – Laboratory Glassware – Volumetric Instruments – Methods
for Testing of Capacity and for Use

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