The determination of the specific heat of Hycar O.R. (oil-resistant)
synthetic rubber is a continuation of a program started some years
ago at the National Bureau of Standards, the object of which is to
furnish thermodynamic data on various types of rubber, both natural
and synthetic, and the monomers from which they are polymerized.
Such data have been obtained for unvulcanized natural rubber [4] 1
and its monomer, isoprene [5], and the equilibrium relationship
between the two has been studied [2]. In the present paper, specific
heat measurements on synthetic rubber Hycar O.R. are described,
and the increase in entropy from absolute zero to 25° C is calculated.
It has been fotmd very useful in previous work to correlate thermal
measuremen ts wi th volume measurements. Anomalies in the en thalpyI
Figures in brackets indicate the literature references at the end of this paper.
87 
88 Journal of Research of the National Bureau of Standm'ds
temperature relation or its derivative are found to be associated with
similar changes in the volume-temperature relation or its derivative.
Measurements of the volume-temperature relation by means of a dilatometer,
therefore, furnish a relatively simple method of determining
the location of transitions and a guide for thermal measurements.
Volumetric work on several samples of synthetic rubber has shown
that they, as well as natural rubber, may undergo transitions [16].
Two types of transition are found. In first-order transitions, the
fundamental properties, such as enthalpy, undergo large changes in a
rather narrow temperature interval. Crystallization and fusion are
first-order transitions. In second-order transitions, the derivatives of
the fundamental properties, rather than the properties themselves,
undergo the large changes. The changes therefore manifest themselves
in the expansivity and in the specific heat, which are the derivatives
of the fundamental quantities, volume and enthalpy.
Natural rubber has been shown, both by thermal measurements [4]
and dilatometric measurements [3, 17] to exhibit both a first-order and
a second-order transition. Many of the synthetic rubbers, however,
unlike natural rubber, show no evidence of crystallization or fusion.
Since the crystallization of a rubber-like substance may make the
thermal investigation very complicated and time-consuming [6], it
was thought advisable to make thermal measurements first on a synthetic
rubber which does not crystallize. Volume measurements [16]
with a mercury-filled dilatometer have failed to show any evidence
of crystallization or fusion in Hycar O.R., and it was selected for the
first thermal studies. The volume measurements showed a secondorder
transition at 250° K.
II. SAMPLE
Hycar O.R., for samples of which we are indebted to the Hycar
Chemical Co. of Akron, Ohio, is an oil-resistant synthetic rubber
which has been on the market since early in 1941. Its chemical
composition has not yet been disclosed by the manufacturer, but it is
reported to be a butadiene co-polymer, and to contain about 2 percent
of phenyl-beta-naphthylamine as a stabilizer [1]. Some of the physical
properties of the compounded Hycar are given by Garvey, Juve, and
Sauser [8].
The density of a sample of unvulcan.ized Hycar O.R. was found to be
0.999 gram per cubic centimeter at 25° C. An analysis of the material
showed that it contained the following: