6 BOILING POINT OF LIQUIDS AND MELTING POINT OF

SOLID MATERIALS

Theory

In a solid material the atom, ions, molecules are bound tightly on their places, they can
vibrate only around their equilibrium position, but do not perform translational motions. The
solid materials have defined shape and volume. With increasing temperature, the energy of
the material components increases and at the melting point they release their position. The
solid material becomes a liquid. In liquids the atoms, ions or molecules are bound less tightly
than in solids. They can perform vibrational, translational and rotational motions, however,
there are weakly connected to their neighbours. They form a surface, also. The volume of a
liquid depends on its density, but its shape depends on the shape of the container, where it is
placed. Increasing the temperature of a liquid, the molecules of the liquid releases its surface
and evaporates, become a gas. In a gaseous material, particles are moving randomly in the
whole volume of the container, affecting each other only slightly, (in an ideal gas do not
affect at all), except the moments of collisions, which are elastic collision, i.e. the sum of the
kinetic energies of the colliding particles is the same before and after the collision. The
volume and shape of the gases depends on the volume and shape of the container, where are
located.
The change of the phase (solid, liquid, gaseous, plasma) of materials are called phase
transitions. They are melting – change of solid to liquid, evaporating – liquid to gaseous and
sublimation – solid to gaseous phase. These phase transitions are so called first order phase
transitions, where the heat capacity of the material have a singularity, i.e. it is not defined. It
is not defined, because despite the fact, that the material is heated (∆𝑄 ≠ 0) its temperature
is not increasing. It means, that the received heat is not transformed into a temperature rise,
but to the change of the state of the material. The relation between the absorbed (released)
heat and the temperature is:
𝑑𝑄 = 𝑐𝑝 𝑑𝑇 𝑑𝑄 = 𝑚𝑐𝑚𝑝 𝑑𝑇 𝑑𝑄 = 𝑛𝑐𝑛𝑝 𝑑𝑇 (1)
where cp ,cmp, cnp is the heat capacity of the system, specific heat capacity and molar heat
capacity, respectively, Q is the heat received (released) by the material, T is the
thermodynamic temperature
1 Boiling of Liquids
Boiling point, temperature at which the pressure exerted by the surroundings upon a liquid
is equalled by the pressure exerted by the vapour of the liquid; under this condition, addition
of heat results in the transformation of the liquid into its vapour without raising the
temperature.
The liquid is changing to a vapour (gas). From the definition is clear, that the boiling point
depends on the surrounding pressure, increases with increasing pressure and depends on the
purity of the material, also.
Usually, boiling points are tabulated at normal pressure (101 325 Pa), and expressed in
Celsius degrees or in kelvins. The boiling points (tv) measured at other pressures (pb) as
normal is necessary to correct according to the equation:
𝑡𝑏 = 𝑡𝑣 + 𝑘(101325 − 𝑝𝑏 ) ( 𝑜𝐶 ) (2)
Where tb is the corrected boiling point and k is the correction coefficient listed in Table 1.
Specific heat (enthalpy) of vaporization (ΔHvs) is amount of heat received by 1 kg of liquid
at given pressure, which is necessary to transform the liquid to its saturated vapour of the
same temperature. Unit J kg-1.
Molar heat (enthalpy) of vaporization (ΔHvm) is amount of heat received by 1 mol of liquid
at given pressure, which is necessary to transform the liquid to its saturated vapour of the
same temperature. Unit J mol-1.
∆𝐻𝑣
∆𝐻𝑣𝑚 = (𝐽 𝑚𝑜𝑙 −1 ) (3)
𝑛
where ΔHv is the heat required to evaporate the liquid and n is the amount of the liquid.
The relationship of the temperature of the phase transition in equilibrium (in this case
vaporization) is expressed with the Clausis-Clapeyron’s equation:
𝑑𝑝 ∆𝐻𝑣𝑚
= (4)
𝑑𝑇 𝑇(𝑉𝑚𝑔 − 𝑉𝑚𝑙 )
where p is the pressure of surroundings (Pa), T is the boiling point (K), Vmg and Vml are the
molar volumes (m3mol-1) of gaseous and liquid phases, respectively. The molar volume of
the liquid phase is negligible in comparison with the molar volume of the gaseous phase (at
𝑔
normal pressure) 𝑉𝑚𝑙 ≪ 𝑉𝑚 , so the difference of the molar volumes can be replaced with the
molar volume of the vapour (Vmg) and substituting for the molar volume of the vapour from
𝑔 𝑅𝑇
the ideal gas law 𝑉𝑚 = we obtain the Clausius-Clapeyron relation in differential form:
𝑝

𝑑𝑝 ∆𝐻𝑚 𝑝
= (5)
𝑑𝑇 𝑅𝑇 2
After integration we obtain the relation of the boiling temperature on the pressure of a liquid:
𝑝 ∆𝐻𝑣𝑚 1 1
𝑙𝑛 𝑝2 = (𝑇 − 𝑇 ) (6)
1 𝑅 1 2

where T1 and T2 are the boiling points (in K) of a liquid at pressures p1 and p2, respectively.

Aim of exercise
To determine the boiling points of unknown liquids and to calculate the corrected boiling points to
normal pressure.

Equiment
Apparatus to determine the boiling point for liquids (Figure 1).

Chemicals
Liquids to determine the boiling point.

Experimental procedure
The apparatus to measure the boiling point of a liquid shown in Figure 1 consists of
evaporating vessel 1, electrical heating body connected to a control unit 2, vapour guide pipe
3, thermometer 4, cooler 5¸ collector of condensed phase 6, discharge valve for condensed
phase 7, overflow pipe 8, discharge valve for liquid phase 9.

Figure 1 The apparatus to measure the boiling point

1. Fill the apparatus with the first liquid through the hole for the thermometer. The surface
 level of the liquid in the evaporating vessel 1 should be 1 cm above the heating body.
Place back the thermometer to the hole.
2. Connect the wires of the heating body to the control unit 2. Put the output voltage on the
control unit to 12-14 V (see arrows on the control unit).
3. Open the water valve for cooling water in the cooler 5.
4. The heating body bring the liquid to a boil. The vapours pass through the guide pipe
around the thermometer to the cooler 5, where are cooled and condensed. The condensed
vapours are collected in the collector 6. When the amount of the condensed vapours
reaches the open of the overflow pipe, they flow back to the evaporating vessel 1. After
certain time (10-15 minute), when the equilibrium is achieved, the temperature on the
thermometer will display constant boiling point of the liquid. Write to the Table 1. the
boiling point of the liquid (tb).
5. Switch off the heating of the apparatus (set output voltage on the control unit to zero,
unplug the wires of the control unit from electricity), pour back the liquid to the stock
flask through the valves 7 and 9 (carefully lift and tilt the apparatus to remove the whole
amount of the liquid through the valve 9).
6. Do not rinse the apparatus with any liquid! Repeat the procedure and measure the boiling
point of the remaining liquids!

Table 1 Determination of the boiling point of liquids

pb =……………. Pa
Corrected Tabulated
Measured 4
Liquid k.10 boiling point boiling
tv (oC)
tb (oC) point (oC)]

Data treatment
Fill in Table 1
- The atmospheric pressure (pb) in Pa, which is available on the barometer in the
laboratory.
- Correction coefficients (k) of liquids from Table 2 on the end of the manual.
- The corrected boiling points of liquids (tb) according to equation 2.
- Tabulated boiling points from the handbook (ask your teacher for the handbook).
Table 2 Correction coefficients (k) of liquids

Liquid k.104 Liquid k.104

acetone 2.9 chlorophorm 2.9
amylalcolhol 2.3 cresol 3.2
benzene 3.2 acetic acid 3.3
ether 2.7 ethyl acetate 3.3
ethanol 2.5 methyl salicylate 4.3

Conclusion
In the conclusion compare the calculated (measured) and the tabulated (from the handbook)
corrected boiling points.

2 Melting point of solids

Melting point (tt) is defined as a temperature, where the liquid and solid phases of a material
coexist in equilibrium at the given pressure.
Heating a solid, chemically pure substance, the temperature of the material is increasing (see
Figure 2) up to certain temperature, when a melted portion (liquid phase) of the material
occurs next to the solid portion. This temperature is called the melting point.

time of heating
Figure 2 Change of melting temperature substance by heating
a – chemically pure substance
b – chemically impure substance

When the heating of the pure substance continues, the added heat is consumed to melt the
solid part of the material until the whole amount is transformed to a liquid and up to this
moment its temperature is stable. This appears as a horizontal part (plateau) on the heating
curve (Figure 2a). As the whole amount of the material is melted, the heating results further
increase of the temperature. (part a and b on the Figure 2).
In the case of melting of a chemically impure substance, the breaks on the curves are not so
sharp (part b on the Figure 2) as in the case of a pure substances. The melting of an impure
material occurs within a temperature range (interval), where the width of this interval
depends on the amount and quantity of the impurities.
Specific melting heat (enthalpy) (ΔHt) is the amount of the heat necessary to melt 1 kg of
a solid material at temperature of the melting point to liquid of the same temperature at the
given pressure. The unit of the specific melting heat is J kg-1.
Molar melting heat (enthalpy) (Htm) is - amount of the heat necessary to melt 1 mole of a
solid material, at temperature of the melting point, to liquid of the same temperature at the
given pressure. The unit of the specific melting heat is J mol-1.
∆𝐻𝑡 (7)
∆𝐻𝑡𝑚 =
𝑛
n is number of moles.
During solidification of a liquid (reverse process of melting) the same amount of heat is
released as during the melting, but the sign of ΔH is opposite. The melting point depends on
the pressure in the environment and it was expressed by Clausius in differential form:
𝑔
𝑙 −𝑉 )
𝑑𝑇 𝑇(𝑉𝑚 𝑚
= (8)
𝑑𝑝 ∆𝐻𝑚

where T is melting point of the material (K), p is pressure of the environment (Pa), Vml, Vmg
are molar volumes of the liquid and gaseous phases (m3mol-1), respectively.
The melting point is measured with a Kofler block (Figure 3). During the determination of the
melting point with a Kofler block, the material is inspected continuously while its temperature is
increasing. The beginning and the end of the melting of the crystallites is recorded, which
corresponds to the interval of the melting of the solid materials. The width of this interval depends
on the purity of the material.
Description of the Kofler block
The Kofler block consists of a heating part, where the sample is heated, a microscope to observe the
changes and of a control part with a display to register the temperature and to control the apparatus.

Aim of exercise
To determine the melting points of solid materials

Equiment: Koffler block

Chemicals: Series of solid samples

Figure 3 Kofler block and capillaries for melting point measurements

Experimental procedure
Follow the manual placed next to the apparatus.

Conclusions
Compare the measured melting points with the tabulated values.

Reference
Oremusová J., Vojteková M., Sarka K.: Fyzika – laboratórne cvičenia pre farmaceutov UK
Bratislava 2009 (in Slovak).

Manual written
RNDr. Alexander BÚCSI, PhD., doc. RNDr. Jana GALLOVÁ, CSc., Ing. Jarmila
OREMUSOVÁ, CSc., prof. RNDr. Daniela UHRÍKOVÁ, CSc.