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Chemistry · Ch 1 — Solutions

Elevation of Boiling Point

1.6.2

Elevation of Boiling Point

A liquid boils at the temperature where its vapour pressure becomes equal to the surrounding atmospheric pressure. Water, for instance, boils at 373.15 K (100 °C) because at that temperature its vapour pressure reaches 1.013 bar (1 atmosphere).

Why the boiling point rises

Adding a non-volatile solute lowers the vapour pressure of the solvent at every temperature. So at the pure solvent's normal boiling point, the solution's vapour pressure is still below atmospheric pressure — it is not yet boiling. To push its vapour pressure back up to 1.013 bar, the solution must be heated to a higher temperature. Hence a solution always boils at a temperature above the boiling point of the pure solvent.

Figure 1.7The vapour pressure curve for solution lies below the curve for pure water. The diagram shows that ΔTb denotes the elevation of boiling point of a solvent in solution.
Fig. 1.7 — The vapour pressure curve for solution lies below the curve for pure water. The diagram shows that ΔTb denotes the elevation of boiling point of a solvent in solution.

Drawn by us to help you understand the concept clearly, and verified to make sure it's accurate. For exams, practice from your textbook's own diagram.

The figure plots vapour pressure on the vertical axis against temperature (in Kelvin) on the horizontal axis. Two upward-sloping curves are shown:

  • The upper curve is for the pure solvent.
  • The lower curve is for the solution (solvent + non-volatile solute).

A horizontal dashed line is drawn at 1.013 bar (standard atmospheric pressure). This line cuts both curves. From each intersection point, a vertical dashed line drops down to the temperature axis:

  • The left vertical line meets the axis at Tb∘T_b^\circ, the boiling point of the pure solvent.
  • The right vertical line meets the axis at TbT_b, the boiling point of the solution.

The horizontal gap between these two temperatures on the x-axis is labelled ΔTb\Delta T_b — the elevation of boiling point.


Physical idea

At any given temperature, the vapour pressure of the solution is lower than that of the pure solvent (Raoult’s law). To make the solution boil — i.e., to raise its vapour pressure up to the external pressure of 1.013 bar — a higher temperature is needed. Hence the solution’s boiling point is higher than the solvent’s boiling point. The figure makes this shift visible: the solution curve must be followed further to the right before it reaches the 1.013 bar line.


Key formula developed from this figure

For dilute solutions, the elevation is directly proportional to the molality mm of the solute:

ΔTb=Kb m\Delta T_b = K_b \, m

where:

  • ΔTb=Tb−Tb∘\Delta T_b = T_b - T_b^\circ is the boiling point elevation (in K),
  • mm is the molality of the solution (in mol kg−1^{-1}),
  • KbK_b is the molal boiling point elevation constant (or ebullioscopic constant) of the solvent, with units K kg mol−1^{-1}.

If w2w_2 grams of solute of molar mass M2M_2 are dissolved in w1w_1 grams of solvent, then

m=1000 w2M2 w1m = \frac{1000 \, w_2}{M_2 \, w_1}

Substituting into ΔTb=Kbm\Delta T_b = K_b m gives the working formula:

ΔTb=Kb×1000×w2M2×w1\Delta T_b = \frac{K_b \times 1000 \times w_2}{M_2 \times w_1} …

Like the lowering of vapour pressure, this elevation depends on the number of solute particles, not their nature.

Defining the elevation

Let Tb0T_b^{0} be the boiling point of the pure solvent and TbT_b the boiling point of the solution. The elevation of boiling point is their difference:

ΔTb=Tb−Tb0\Delta T_b = T_b - T_b^{0}

The elevation is proportional to molality

Experiments on dilute solutions show that ΔTb\Delta T_b is directly proportional to the molal concentration of the solute:

ΔTb∝m\Delta T_b \propto m

ΔTb=Kb m\Delta T_b = K_b\,m

where mm is the molality (moles of solute per kilogram of solvent) and KbK_b is the constant of proportionality.

Important

KbK_b is the Boiling Point Elevation Constant or Molal Elevation Constant (also called the ebullioscopic constant). Its unit is K kg mol−1\text{K kg mol}^{-1}. Its value depends only on the solvent; values for common solvents are tabulated separately.

Building the molar-mass formula

If w2w_2 gram of a solute of molar mass M2M_2 is dissolved in w1w_1 gram of solvent, the molality is

m=w2/M2w1/1000=1000×w2M2×w1m = \frac{w_2 / M_2}{w_1 / 1000} = \frac{1000 \times w_2}{M_2 \times w_1}

Substituting this into ΔTb=Kb m\Delta T_b = K_b\,m: …