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Principle:
The boiling point of a solution is
always higher than that of the pure
solvent. The dependence of the tem-
perature difference (elevated boiling
point) on the concentration of the
solute can be determined using a
suitable apparatus.
PHYWE series of publications Laboratory Experiments Physics PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen 23403-00 1
LEP
3.4.03 Boiling point elevation
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The dependence of the boiling point elevation of water on the Theory and evaluation
concentration can be demonstrated for each substance in one If a small amount of substance B, which has a negligible
experiment by successively adding known amounts of the vapour pressure, is dissolved in a pure solvent A, the depres-
same substance. First, weigh the dry inner vessel exactly, and sion of the vapour pressure of A can be calculated using
then add 40 ml water; assemble the apparatus and heat it up. Raoults law - assuming that the solvent demonstrates ideal
The heating rate is controlled with the power control. The tem- behaviour. This depression of the vapour pressure is seen in
perature in the inner vessel is displayed on the digital temper- the experiment as an increase in the boiling point of the solu-
ature meter in degrees Celsius. When the boiling point is tion compared with the pure solvent A.
reached, lower the heating hood for a short time until boiling
stops. In this way the condensate on the outer vessel returns For each equilibrium point, the chemical potential of the
to the round flask. Then raise the heating hood again. When vapour phase NAI is equal to the chemical potential of the sol-
boiling recommences, close the pinchcock. The (slightly super- vent NAI (NAg = NAI ) The chemical potential of the solvent in the
heated) steam now flows through the water in the inner vessel. solution is
Set the digital temperature meter to measure the change in
temperature %T over time in accordance with instruction man- mlA m0A l RT lnxA (1)
ual (accuracy of temperature measurement 0.01 K) and wait
until the value displayed remains constant. By depressing the where m0A lis the chemical potential and xA is the amount of
%T button again, the relative boiling temperature can be reset substance of the pure solvent. At boiling point, NAg is also equal
0g
to 0 K and the device then shows the temperature difference to to the chemical potential mA of the pure solvent vapour.
this value directly. Now carefully open the inner vessel (screw If NA = NA, then the following is obtained:
g I
cap), add the first substance pellet, and reclose the opening
immediately. The temperature first drops slightly and then rises m0A g m0A l RT lnxA (2)
again as soon as the pellet has dissolved. When the value has
Since the chemical potential of pure substances is identical to
again become constant, record it together with the exact mass
the molar free enthalpy G0 , equation 2 becomes:
of the pellet. Repeat this procedure for the next portion of the
substance. After five concentration steps have been meas- G 0A g G 0A l RT lnxA (3)
ured, open the pinchcock and switch off the heating. Now
remove the inner vessel, dry its outer surface, remove the tem- From the Gibbs-Helmholtz equation
perature probe and the pipe; then re-weigh the inner vessel.
The mass of the water is now equal to the last measured value d(G>T) H
= 2 ; p = const. (4)
less the mass of the empty vessel and the masses of the five dT T
substance pellets. For each substance plot the increase in
we can differentiate equation (3) to obtain
boiling point against the quotient of the mass of the dissolved
substance and the mass of water as shown in Fig. 2.
H 0A l H 0A g vH d InxA
2
2
= (5)
RT RT dT
The enthalpy of vaporisation A~H can be considered con-
stant for small temperature changes. Integration of (5)
between the limiting values for the pure solvent (xA = 1, T = T0)
and for solution (xA, T ) results in
vH 1 1 vH T T0
lnxA = a b= a b (6)
R T0 T R TT0
vH T T0
a b = In (1 xB) (7)
R TT0
vH Tv 1 2 1 3
= xB + x + x (8)
2
RT 0 2 B 3 B
2
Fig. 2: Example of a measurement: boiling point increase as RT0
%Tv = xB (9)
function of concentration of table salt in an aqueous vH
solution.
2 23403-00 PHYWE series of publications Laboratory Experiments Physics PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen
LEP
Boiling point elevation 3.4.03
-00
For dilute solutions, a good approximation of the amount of Under certain conditions, the determination of molar masses
substance is the ratio (mBMA / mBMB). MA, MB and mA, mB are using ebullioscopy can therefore only supply the apparent
the molar masses and weighed masses of solvent A and molar mass Ms which has then to be converted using
solute B, respectively.
MB
Ms = (13)
2
RT0 mBMA
2
RT0 MA mB 1 (z 1)a
%Tv = = (10)
vH mAMB vH mA MB
Similar considerations apply to the associated particles in
solution.
Finally, the fraction mBMA / mBMB can be considered to be
equal to m/1000, where m is the molality, i.e. the amount of
solute in 1000 g of solvent.
n = nB (1 + (z 1)B) (12)
PHYWE series of publications Laboratory Experiments Physics PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen 23403-00 3
LEP
3.4.03 Boiling point elevation
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4 23403-00 PHYWE series of publications Laboratory Experiments Physics PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen