NAME : AHMER MEHMOOD

ROLL NO : 206661507_030
SUBJECT : PHYSICAL CHEMISTRY ||

Title: Measurement of Conductance and

Kohlrausch's Law

Introduction:: Conductance is a fundamental property that characterizes the ability of a substance or

solution to conduct an electric current. It plays a crucial role in various fields, including chemistry,
physics

Measurement of conductance: Conductance measurement techniques

can be broadly classified into two categories: direct methods and
indirect methods. These methods differ in their approach to measuring
the conductance or conductivity of a substance

Direct Methods
Direct methods involve directly measuring the conductance of a substance or solution
using a conductance meter or conductivity cell. These methods provide real-time and
accurate conductance measurements. Some commonly used direct methods include:
a. Cell or Bridge Method: In this method, a conductivity cell or bridge is employed to
measure the conductance of the solution. The cell consists of two electrodes, usually
parallel plates or cylindrical probes, immersed in the solution. The conductance is
determined by measuring the current passing through the solution when a voltage is
applied across the electrodes. The conductance meter directly measures the current and
voltage, and calculates the conductance using Ohm's law.
b. Four-Electrode Method: The four-electrode method, also known as the Kelvin or
Guard ring method, is used for accurate conductance measurements of low-conductivity
solutions. It involves using two pairs of electrodes: one pair applies the voltage, while
 the other pair measures the resulting current. The four-electrode setup minimizes errors
caused by electrode polarization and contact resistance, leading to more precise
conductance measurements.

INDIRECT METHODS
Indirect methods of conductance measurement estimate the conductance or
conductivity based on other measurable properties or parameters. These methods are
often used when direct measurements are not feasible or when estimating conductance
indirectly is more practical. Some commonly used indirect methods include:
a. Resistance Measurement: Conductance and resistance are reciprocal quantities,
meaning that conductance (G) is equal to the inverse of resistance (R). Indirectly
measuring resistance using a resistance meter and then converting it to conductance is
a simple and widely used method. Conductance can be calculated as G = 1/R.
b. TDS (Total Dissolved Solids) Measurement: Total Dissolved Solids refers to the sum of
all inorganic and organic substances dissolved in a solution. TDS meters estimate the
conductivity of a solution based on the correlation between TDS and conductivity. TDS
measurements are converted to conductivity measurements using empirical conversion
factors or calibration curves.

TITRATIONN METHOD
Titration methods involve determining the concentration of an analyte in a solution by adding a
titrant of known concentration until a chemical reaction reaches completion. Conductometric
titration is a technique where conductance is measured during the titration process to detect the
endpoint of the reaction. Changes in conductance indicate changes in ion concentration,
helping to determine the equivalence point.

Factors influencing accurate conductance measurements

Accurate conductance measurements are influenced by various factors that can affect the
reliability and precision of the results

1. Temperature: Conductance measurements are temperature-dependent because the

conductivity of a substance changes with temperature. It is crucial to control and
monitor the temperature of the solution during measurements. Conductance meters
often include built-in temperature sensors to compensate for temperature variations
and provide temperature-corrected conductance values.
2. Electrode Condition: The condition and cleanliness of the electrodes can significantly
impact conductance measurements. Any contamination or oxidation on the electrode
 surfaces can lead to inaccurate readings. It is essential to clean and maintain the
electrodes properly to ensure reliable and consistent measurements.
3. Electrode Polarization: Electrode polarization occurs when charged ions accumulate at
the electrode surfaces, creating a potential barrier that hinders the flow of current. This
phenomenon can affect conductance measurements, particularly in low-conductivity
solutions. Techniques such as using alternating current (AC) instead of direct current
(DC) or employing four-electrode methods can minimize electrode polarization effects.
4. Solution Composition: The conductivity of a solution is influenced by the
concentration and type of ions present. The conductance of an electrolyte
solution generally increases with increasing ion concentration. Additionally, the
type and nature of the ions affect their mobility and conductance. It is important
to consider the solution composition and concentration when interpreting
conductance measurements.
5. Electrical Interference: External electrical interference, such as electromagnetic
noise or stray currents, can introduce errors and fluctuations in conductance
measurements. Proper shielding, grounding, and isolation techniques should be
employed to minimize these interferences and ensure accurate readings.
6. Calibration: Conductance meters should be calibrated regularly using standard
reference solutions of known conductance or conductivity. Calibration ensures
the accuracy and reliability of the instrument's measurements. Proper calibration
procedures and adherence to calibration schedules are essential for obtaining
accurate conductance data.
7. Sample Handling: Proper handling of the sample solution is crucial to avoid
contamination and ensure accurate conductance measurements. Contaminants or
impurities in the solution can affect conductivity and lead to erroneous results.
Clean glassware, careful sample preparation, and appropriate storage conditions
are necessary for accurate measurements.

Kohlrausch's Law

Kohlrausch's Law, named after the German physicist Friedrich Kohlrausch, is a

fundamental principle in electrochemistry that relates the conductance of an
electrolytic solution to the concentration and mobility of its constituent ions.
This empirical law provides insights into the behavior of electrolytes and helps
in understanding the conductivity of solutions.
Kohlrausch's Law states that the molar conductance of an electrolyte at infinite
dilution (also known as the limiting molar conductance, Λ°) is the sum of the
molar conductances of its individual ions, each multiplied by their respective
concentration. Mathematically, it can be expressed as:

Λ°(AB) = Λ°(A+) + Λ°(B-)

where Λ°(AB) is the limiting molar conductance of the electrolyte AB, Λ°(A+) is
the limiting molar conductance of the cation A+, and Λ°(B-) is the limiting
molar conductance of the anion B-.

MATHMATICAL REPRESANTATION
To derive the mathematical representation of Kohlrausch's Law, we start by
considering a binary electrolyte, AB, which dissociates into a cation A+ and an
anion B-.

Let's assume that the concentration of the electrolyte AB is C, and the

concentration of each ion, A+ and B-, is C+ and C-, respectively.

The molar conductance of the electrolyte AB at infinite dilution is represented

as Λ°(AB). Similarly, the molar conductance of the cation A+ and the anion B-
at infinite dilution are represented as Λ°(A+) and Λ°(B-), respectively.

According to Kohlrausch's Law, the limiting molar conductance of the

electrolyte AB is equal to the sum of the limiting molar conductances of its
constituent ions. Mathematically, we can express this as:

Λ°(AB) = Λ°(A+) + Λ°(B-) ----(1)

Now, the conductance of an electrolyte is directly proportional to the

concentration of ions present in the solution. Therefore, we can write the
conductance (G) of the electrolyte AB as:

G(AB) = Λ(AB) * C ----(2)

where Λ(AB) represents the molar conductance of the electrolyte AB at a

particular concentration C.
Similarly, the conductances of the cation A+ and the anion B- can be
expressed as:

G(A+) = Λ(A+) * C+ ----(3) G(B-) = Λ(B-) * C- ----(4)

Since the total conductance of the electrolyte AB is the sum of the

conductances of its constituent ions, we have:

G(AB) = G(A+) + G(B-) ----(5)

Substituting equations (2), (3), and (4) into equation (5), we get:

Λ(AB) * C = Λ(A+) * C+ + Λ(B-) * C- ----(6)

Now, if we consider the conductivities of the ions (κ) instead of the molar
conductances, we know that κ = Λ/C. Therefore, equation (6) can be rewritten
as:

κ(AB) = κ(A+) * C+ + κ(B-) * C- ----(7)

where κ(AB) represents the conductivity of the electrolyte AB, and κ(A+) and
κ(B-) represent the conductivities of the cation A+ and anion B-, respectively.

Equation (7) is the mathematical representation of Kohlrausch's Law for a

binary electrolyte. It relates the conductivity of the electrolyte to the
conductivities and concentrations of its constituent ions.

SIGNIFICANCE OF KOHLARAUSCH LAW

The significance of Kohlrausch's Law lies in its ability to provide valuable information
about the conductivity and behavior of electrolytic solutions, particularly at low
concentrations. It offers the following key insights:

The significance of Kohlrausch's Law lies in its ability to provide valuable information
about the conductivity and behavior of electrolytic solutions, particularly at low
concentrations. It offers the following key insights:
1. Ionic Conductivity: Kohlrausch's Law allows for the estimation of the molar conductance
of individual ions in a solution by subtracting the conductance of one ion from the total
conductance of the electrolyte. This provides an understanding of the contribution of
each ion to the overall conductivity and helps in studying the mobility and behavior of
ions in solution.
2. Electrolyte Strength: The limiting molar conductance of an electrolyte at infinite dilution
provides information about its dissociation and ionization behavior. Strong electrolytes,
which completely dissociate into ions in solution, exhibit higher limiting molar
conductance values than weak electrolytes, which only partially ionize. Kohlrausch's Law
assists in quantifying the degree of dissociation or ionization for different electrolytes.
3. Concentration Dependence: While Kohlrausch's Law is derived for infinite dilution
conditions, it can be applied to solutions of finite concentrations as well. By considering
the conductance of an electrolyte at different concentrations, it is possible to analyze
the concentration dependence of its conductance and assess deviations from ideal
behavior.
4. Solution Properties: Kohlrausch's Law aids in understanding the effect of temperature,
solvent properties, and electrolyte concentration on the conductance of solutions.