DILUTION OF LITHIUM CHLORIDE 517 
The calculated electromotive forces of cells involving* trans- 
ference are obtained by making the proper substitutions in equa- 
tion (5) ; for cells without transference similar substitutions are 
made in equation (6). The molecular conductivities of lithium 
chloride which have been substituted in these equations are taken 
from the work of Greene 14 for the aqueous solutions. Those for 
solutions in ethyl alcohol are taken from the work of Jones and 
Turner. 15 No conductivity data for solutions of lithium chloride 
in methyl alcohol at this temperature are to be found in the 
literature. This is not essential, however, since the calculated 
electromotive forces in methyl alcohol would doubtless show 
results similar to those which have been found for solutions in 
water and ethyl alcohol. 
From theoretical considerations (Equation 6) it is evident that 
the magnitude of the calculated electromotive force for cells 
without transference is dependent solely upon the ratio of the 
ionic concentrations as calculated from electrical conductivity. 
On the other hand, the observed electromotive forces for cells 
without transference are determined by the ratio of the activity 
of the solutions, and more particularly the activity of the ions, 
about the electrodes. For cells with transference the value of 
the electromotive force measured is dependent not only upon 
the relative activity of the ions in the two solutions, but also 
upon the transport numbers of these ions. The electromotive 
force of cells with transference is useful in this investigation 
only as a factor for the determination of the transport number 
(Equation 3). All other calculations are made from the values 
of the electromotive forces without transference. 
The transport number of the lithium ion increases with in- , 
creasing dilution in each of the solvents studied. For a given 
change in dilution this increase is least in the aqueous solutions 
and greatest for solutions in ethyl alcohol. The values of the 
transport numbers determined by this method are the average 
values between the two concentrations of the electrolyte consti- 
tuting the cell. It is, therefore, difficult to make a direct com- 
parison with other published results. Table II gives the values 
obtained by Kohlraush and Holborn 16 for the transport number 
of the cation of lithium chloride in aqueous solutions at 25°. 
“Trans. Chem. Soe., 93, (2) 2042, 1908. 
15 Am, Chem. Jour., 40, 558, 1908. 
lc Leitvermogen der Electrolyte, p. 201. 
