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Worked Examples · Example 2.6
Q.

The molar conductivity of KCl solutions at different concentrations at 298 K are given below:

cc / mol L−1mol\ L^{-1}Λm\Lambda_m / S cm2 mol−1S\ cm^2\ mol^{-1}
0.000198148.61
0.000309148.29
0.000521147.81
0.000989147.09

Show that a plot between Λm\Lambda_m and c1/2c^{1/2} is a straight line. Determine the values of Λm0\Lambda^0_m and AA for KCl.

CBSENCERTSubjective· 3mImportance★★★★★
5% · 6/115 Questions
✓ Free question
Figure 2.7
Figure 2.7

For strong electrolytes like KCl, molar conductivity varies linearly with the square root of concentration (Kohlrausch's law). Plotting Λm\Lambda_m vs c1/2c^{1/2} gives a straight line; the book reads its intercept as Λm0=150.0 S cm2 mol−1\Lambda_m^0 = 150.0\ \text{S cm}^2\text{ mol}^{-1} and its slope gives A=87.46 S cm2 mol−1 (mol L−1)−1/2A = 87.46\ \text{S cm}^2\text{ mol}^{-1}\text{ (mol L}^{-1})^{-1/2}.

The key idea here is Kohlrausch's law of independent migration of ions. For strong electrolytes, as you dilute the solution, ions move more freely because interionic attractions weaken. The molar conductivity Λm\Lambda_m therefore increases on dilution — and, plotted against the square root of concentration, it decreases linearly as c\sqrt{c} rises. This linear relationship is the hallmark of a strong electrolyte.

Why c\sqrt{c}? Because the Debye–Hückel theory shows that the ionic atmosphere dragging on a moving ion has a radius proportional to 1/c1/\sqrt{c}. So the retarding effect scales with c\sqrt{c}, and conductivity rises as c\sqrt{c} falls.

The equation is:

Λm=Λm0−Ac\Lambda_m = \Lambda_m^0 - A \sqrt{c}

where Λm0\Lambda_m^0 is the limiting molar conductivity (at infinite dilution) and AA is a constant for the electrolyte.

Let's test this with the given data.

  1. Convert the data to c\sqrt{c} values.

    cc (mol L⁻¹)c\sqrt{c} (mol L⁻¹)1/2^{1/2}Λm\Lambda_m (S cm² mol⁻¹)
    0.0001980.01407148.61
    0.0003090.01758148.29
    0.0005210.02283147.81
    0.0009890.03145147.09
  2. Plot Λm\Lambda_m against c\sqrt{c}.

    The points fall on a straight line: as c\sqrt{c} increases, Λm\Lambda_m decreases linearly. This confirms Kohlrausch's law for KCl.

  3. Find AA (slope magnitude).

    The slope of the line is −A-A:

slope=147.09−148.610.03145−0.01407=−1.520.01738=−87.46 S cm2 mol−1 (mol L−1)−1/2\text{slope} = \frac{147.09 - 148.61}{0.03145 - 0.01407} = \frac{-1.52}{0.01738} = -87.46\ \text{S cm}^2\text{ mol}^{-1}\text{ (mol L}^{-1})^{-1/2}

So A=87.46 S cm2 mol−1 (mol L−1)−1/2A = 87.46\ \text{S cm}^2\text{ mol}^{-1}\text{ (mol L}^{-1})^{-1/2}.

  1. Find Λm0\Lambda_m^0 (the intercept). Extending the straight line to c=0\sqrt{c} = 0 (infinite dilution), NCERT reads the intercept from the graph as:

Λm0=150.0 S cm2 mol−1\Lambda_m^0 = 150.0\ \text{S cm}^2\text{ mol}^{-1}

Tip

You don't need to draw the graph perfectly in an exam — just show that the points satisfy a linear relation by computing the slope between successive pairs. If the slopes are nearly constant, the plot is a straight line.

Watch out

A common mistake is to plot Λm\Lambda_m against cc instead of c\sqrt{c}. That curve is not linear — it bends. Always use c\sqrt{c} for strong electrolytes.

Note

NCERT reads Λm0=150.0\Lambda_m^0 = 150.0 from its graphical extrapolation. If you instead fit the four points algebraically (least squares, or point-slope from the first point: 148.61+87.46×0.01407=149.84148.61 + 87.46 \times 0.01407 = 149.84), you get Λm0≈149.8 S cm2 mol−1\Lambda_m^0 \approx 149.8\ \text{S cm}^2\text{ mol}^{-1} and A≈87.5A \approx 87.5 — essentially identical to the printed values; the difference is only graphical rounding of the intercept.

✓Final answer

The plot of Λm\Lambda_m vs c1/2c^{1/2} is a straight line, giving Λm0=150.0 S cm2 mol−1\Lambda_m^0 = 150.0\ \text{S cm}^2\text{ mol}^{-1} and A=87.46 S cm2 mol−1 (mol L−1)−1/2A = 87.46\ \text{S cm}^2\text{ mol}^{-1}\text{ (mol L}^{-1})^{-1/2} for KCl at 298 K.

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