Temperature Dependence of Absorbance in Ultraviolet

Spectra of Organic Molecules

V. A. YARBOROUGH, J. F. HASKIN, and W. J. LAMBDIN
Carbide and Carbon Chemicals Co., Division o f Union Carbide and Carbon Corp., South Charleston, W. V a .

The ultraviolet spectra of molecules change with the
temperature. Quantitative temperature coefficients
of absorbance, however, are not generally available.
The variations of ahsorbance with temperature of the
sample in the ultraviolet spectra of 19 typical organic
compounds have been studied at increments between
5" and 33" C., employing methanol and iso-octane as
diluents. The variation ranges from O.Oo/c per ' C.
for acetone and 2,Shexanedione to 0.7470 per O C. for
toluene. A Car? spectronieter has been fitted with
special cells that permit contrnlled 3 ariation of the
temperature of the sample.
weight %). Thus, the instrumental fluctuations and variations
in absorbance with ambient temperature exceeded the manipu-
latory deviations. These variations were not observed, however,
when analyses were repeated within intervals of a few minutes.
Similar experiments with spectrometric analyses of an aliquot
of acetone gave an average daily deviation of only 0.5 weight %.
The difference in the behavior of benzene and of acetone may be
explained by their temperature coefficients of absorbance. The
coefficients for benzene are 0.50 and 0.48% change in absorb-
ance per degree centigrade iii methanol and in iso-octane, respec-
tively; the coefficient for methanol is 0.00 for both diluents. -4~-
cordingly, quantitstire evaluation of temperature coefficients w : ~
undertaken for other typical organic moleculefi.

T HE absorption spectra of molecules in the ultraviolet spec*-

tral region are known to change with temperature. Arnold
and Kistiakowsky ( 1 ) h a r e observed profound sharpening of the Table I. Temperature Coefficients of .4bsorbance
bands exhibited by aromatic compounds when the temperature in Ultraviolet Spectra
Temperaturr Decrease in
was lowered to 80" I<. This effect also has been utilized in the Coefficient Absorbance. % /
investigation of the origin of bands by Sklar (10). The molecular Wai-e Length. n i p of A b s o ~ b a n c e ~ C.b
hleth- Iso- Meth- Iso- Meth- Iso-
structure of dyes has hecn studied by Sheppard and Brigham Diluent anol octane and ortane anol octane
(9) who examined the spectra of dyes a t low temperatures. Compound
Such spectral changes can provide unique information in the Benzene 254 4 2.54.8 0 00lj2 0 00i12 0 50 0 48
Toluene 268.8 268.8 0 .008(i 0 0085 0 74 0 71
identificztion of different molecules whose spectra are simihr o-Xylene 270. !+ 271.1 0.0078 0 0073 0 (11 0 59
m-Xylene 2 7 2 . (i 272.7 0,0070 0 0071 0 5R 0 57
a t room temperaturee.g., the work of Bowden and Snow ( 5 ) p-Xylene 274, li 2 7 4 . li 0 0Oiii 0 OOfi9 0 55 0 55
in the isolation of vitamin -4. An apparatus for thr quanti- Benzoic acid 280.3 28.1 0 0021 0 0018 0 09 0 04
Benzaldehyde 288 0 0020 0 06
tative determination of Fpectra of subetances at low tempera- Nitrobenzene 2B!l 253 0..0017 0 0:
Aniiine 254 287 0.0020 0 08
tures is described by Beale :md Roe ( d ) , who also list nunicrous Acetone 2i-l 270 0.0004 0 0009 0 00 0 00
references. Ethyl aceto-
acetate 244 243 0 0061 0 0014 0 49 0 00
Temperature dependence of absorption in ultraviolct and visi- 2,4-Pentane-
&one 273 2il 0 0068 0 0030 0 56 0 16
ble spertra of some molecules and ions influences the reproduci- 2,j-Hpxane-
bility of' analytical spcctropliotonietric application,?. Bastian dione 270 272 0 0007 0.0008 0.00 0.00
p-Quinone 242 210 0,0020 0,0023 0.08 0.09
( S ) , Iiiirtum and van Ha1l):in ( 7 ) , blulterji, Bhattacharji, and 2,4-Hexadienal 271 ?fil 0,0019 0.0016 0.07 0.02
Dhar (8),Haupt ( 6 ) , and -lyres and Tuffly (a)!h a r e reported 1.3-Pentadiene
Cyclopenta-
223 224 0.0014 0,0020 0.02 0.06
various manifestations of this phenomenon. diene 24'2 241 0.0018 0.00li 0.06 0.03
Pl-ridine 257 25G 0.0027 0,0014 0.1.5 0 00
T h e attention of tile autliors has heen directed toward the
a Variation in absorbancr per C. divided by absorbance a t 25' C .
influence of temperature o n ultraviolet spectra during an in- b Corrected for cuhiezrl mlmnsion of diluent
ve3tigation of the reproducibility of analyses of benzeiie. Five
aliquots of a sample of nitration grade ben7ene {vwe prepaied
in iso-octane and analyzed spectrometrically o n 6 consecutive 41'PiR 4TUS :AND PROCEDURE
operating days. The results of the analyses indicated greater A Cary hlodel 11 recording spectrometer was fitted with Rpe-
deviation for aliquots from day to day (1.0 weight %) than the
cia1 cells for the me:tsurements of absorption of samples at variouR
average deviation among the aliquots on a spevihc day (0.0 temperatures. The conventional quart8z cells (100-mm. optical
p:tthi were equipped with heat transfer jackets and
expansion bulbs as illustrated in Figure 1. The
temperature of the liquid sample was controlled
by the flow of water from a regulated bath through
the jackets. Covers for the cell compartment's
were constructed with ports to permit passage of
the n-atcr lines. Measurements made with an
immewed thermocouple indicated that the sample
t,emperature closely approached that of t,he thermo-
stat aft,er an equilibrium period of 10 minutcs,
i~-hich\ y a p observed in all of the studies. The com-
plete assembly with cells removed from the com-
partment is illustrateti in Figure 2.
Thr compounds \yere dissolved in the appro-
priate solvents and diluted to roncent,rafions that
rrhihit,ed an absorbance of npprosimat,ely 0.7 a t
25' C. in the 100-mm. cells. The temperat,ure of
1910x100 nm W T L t,he regulated bath then as varied in increments of
2" C. from 5' to 33" C. .lfter each temperature
had been attained in the bath, a 10-minute interval
Figure 1. Quartz Cell Constructed for Determination of Tempera- was allon-ed to enable the SolUtion i n the ('ell to
ture Dependence of Absorbance in Ultraviolet Spectra of Liquids come to equilibrium.
1576
V O L U M E 26, NO. 10, O C T O B E R 1 9 5 4
Corrections for the cubical expansion of the diluents were de-
ducted from the percentage variation of absorbance. These
values accounted for the virtual dilution of the solution that
accordingly reduced the absorbance. For methanal this value
u;asO.l2%per ' C . ; for iso-octane, 0.140/,per C.
RESULTS
The temperature coefficients of nhsorbanoe in the ultraviolet
spectral region have hren determined for typical organic mole-
cules a t temperatures in the range, 5' to 33" C. For most of
these compounds of varied chromophoric structure, the ahsorb-
anee decreases linearly with increasing sample temperature.
The coefficients for representative organic compounds are
presented in Tahle I. T h e eflect,s of an acid and of B base on the
coefficients of phenol, nitroheneene, and miline a.re depicted in
Tahle 11. T h e corrected coefficients m n ~ from
e 0.0 for acetone
and for 2,5-hexanedione to O . i 4 % decrease in itbsorlmnce per
degree centigrade for tnluenr (dissolved in methanol).
Plots of the nhsorl,nrico of lmsene versus temperiiture are
presented in Figure S. The curves are positioned by the method
of least squares. Apparently, within the observed range, the
absorbance is an approsimitelj- linear function of thc tempera-
ture.
In scanning the spectra of the various compounds discussed
herein, recordings usually were made of only the spectral region
necessary to establish a base line for the pertinent absorption
mayimum. T h e complete spectrum of benzene, houwer, was
recorded a t temperatures ranging from 13" to 33' C. I n this
range the temperature coefficient of ahsorhance increased ap-
proximately by 2% of the corrected value per millimicron
(248.6 to 260.6 m# region).
DISCUSS103
Of the etructures investigated in this study, the coefficients
for the aromatic hydrocarbons, and for auch chelate formers as
1577
$I. .*
The similarity in the temperature coefficients of absorbance
for solutions of 2,4pentanedione and of ethyl acetoacetate in
methanol may he explained hy their chelation. The high res-
onance energy in these forms sets these compounds apart from
the other aliphatic substances. With higher temperatures, per-
haps, the increased interaction of the polar solvent (methanol)
with the solute tends to reduce the degree of tautomeriaation.
The shsorhance is accordingly diminishcd. I r a nonpolar solvent
(isa-mtanc), on the contrary, elevation of temperature producea
only minor reductions of ahsorhance for these two molecules.
The dependence of the ahwrhmce on the temperature then
is due in part to a corresponding variation of the soluksolvent
interaction. Also, a t diminished temperatures the rotational
transitions decrease and the electronic-vibrational bands tend
to become more sharply defined. This sharpening of the maxima
increases the absorbance for moderate decreases in temperature.
A t extremely low temperatures (80" IC) Arnold and Kistiakow-
sky ( 1 ) have observed only the lines associated with the de*
tronic-vibrational transitions of benzene. Generally, this effect
is not exhibited by aliphatic substances.
T h e symmetry and the dipole moments of aromatic molecule8
evidently are not primary factoisin determining these Coefficients.
Moreover, coefficients of the five aromatic hydrocarbons are in-
congruous with other physical properties of the molecules--e.g.,
melting points, bailing points, and refractive indices. The tem-
1578
perature coefficients appear to be in qualitative agreement with
the relative chemical reactivity of toluene, the xylenes, and
benzene.
coYcLusloYs
The temperature coefficient of absorbance in the ultraviolet
spectral region is a significant factor for certain aromatic hydro-
carbons and some chelated aliphatic oxygenated compounds.
Precise quantitative analyses of mixtures that contain any of
these substances require control of the temperature of the sample,
or empirical corrections for ohserved deviations in temperature.
For the determination of other compounds noted herein, the
variation of absorbance with temperature is usually negligible
compared with the normal manipulatory errors.
Determination of Sodium and Potassium Oxides by Flame Photometry
In Portland Cement Raw Materials and Mixtures and Similar Silicates
C. L. FORD
Analytical Laboratories, Research and Development Division, Portland Cement Association,
A method was needed whereby acid-insoluble silicates,
such as are used in the manufacture of portland ce-
ment, could be brought rapidly into solution for deter-
mination of sodium and potassium oxides by flame
photometry techniques in common use for cement.
The desired results were attained by sintering and ex-
tracting the material by the classical J. Lawrence
Smith method, then removing the unknown amount
of calcium in the extract and substituting a known
amount (plus hydrochloric acid) approximating that
found in the standard solutions used in the method for
cement. The alkali contents obtained by flame pho-
tometry were in good agreement with those obtained by
comparable gravimetric analyses of the same silicates.
I n using the new method it is not necessary to prepare
special solutions or otherwise alter the flame pho-
tometer technique used for portland cement. The
time requirements are much less than for gravimetric
determination of alkalies in silicates.
T HE increasing interest in the alltali content of portland
cement has led to an increasing demand for determination of
the sodium and potassium oxide content of cement, and the raw
materials from which it is made, and an increasing need for 1111-
proved analytical methods. This need has been met, in the case
of cement, bv an .4STM tentative method ( 2 ) using flame pho-
tometry. Similar short methods (not ASTlI) for determining the
alkali content of cement raw mateiials and tnixtures, or similar
silicates, were incomplete or not designed for the cement testing
laboratory. The study reported herein was undertahen to de-
velop for the cement chemist an accurate method of analysis of
raw materials by flanir photometry which would require the
minimum of special preparation and manipulation.
G E b E R 4 L COY SIDER4TION S
Before any niaterial can be analj zed by the flame photometer,
the desired constituents must be in solution. The nearly coni-
plete solubility of cement in dilute hydrochloric acid mahes pos-
sible the relativelv simple procedure of the tentative ASTLI flame
ANALYTICAL CHEMISTRY
LITERATURE CITED
(1) .iriiold, L. B., Jr., and Kistiakowsky. G . B.. J . Am. Chem. Soc.,
54, 1713 (1932).
(2) Ayres, G. H., and Tuffly, B. L., A B . ~ LCHEY.,
, 23, 788 (1951).
(3) Bastian, R., Ibid., 25,259 (1953).
(4) Beale, R. N., and Roe, E. 11.F., J . Sci. Instr., 28, 109 (1951).
(5) Bowden, F. P., and Snow, C. P., Proc. Rog. Soc. ( L o n d o n ) ,
115B,261 (1934).
(6) Haupt, G. W., J . Rescarch Natl. Bur. Sfandards, 48, 414 (1952)
(RP 2331).
(7) Kortum, G., and Halban, -4.v., 2. physik. Chena., 170A, 212
f1934).
(8) JIukerj;, B. K., Bhattacharji, A. K., and Dhar, W. R., J . PhUs.
Chem., 32, 1834 (1938).
(9) Sheppard, S.E., and Brigham, H. R., J . Am. Chem. Soc., 66.
380 (1944).
(10) Sklar, A. I,., J . Chem. Phys., 5 , 669 (1937).
R L G L IE\ D for review J l a r c h 15, 1934. Accepted July 1, 1954
33 W e s t Grand Ave., Chicago 10,111.
photometer method ( 2 ) . The partial inPo1ubility of most cement
raw materials (except high-grade limestones) requires some other
method of dissolving the alkalies. .Z majority of investigators
( 3 , 4 , 6 - 8 , 1 0 ) of photometric procedures have used some modifica-
tion of the well-known J. Lawrence Smith sintering procedure to
decompose the sample, followed by est,racting the sinter cake
n-ith Imter. [This procedure is used in the BSTM referee
method ( I ) , in which the alkalies are finally determined gravi-
metrically.] The water extract contains the alkalies and varying
amourit,s of calcium derived largely from the calcium carbonate
used in the sintering procedure. The aniount varies with the
way the sinter cake is extracted.
The authors principal efforts have been directed toward de-
veloping a method which would be accurate and would permit
the cement chemist to use the same standard solutions that are
used for cement testing bj- flame phot,ometry. Cement labora-
tories using the flame phot,omet,erare likely to itock such standard
solutions; hence if solutions of the ran- materials could be pre-
pared to contain similar amounts of calcium. same solutions could
be used for standardization of the instrument in testing both
cements and raw materials. This mag be done by removing
the unknown amount of calcium present in the sinter cake ex-
tract and replacing it with a known amount approximately the
same as that present in the cement solutions used for test ac-
cording t,o the hSTN photometric method.
PROCEDURE
Preparation and Analysis of Sample. Weigh 0.5 to 5.0 grams of
the finely pulverized raw material and mix it with 0.5 to 1.0 gram
of ammonium chloride by grinding the two together in an agate
or mullite mortar for 3 minutes (for choice of sample size see the
discussion of procedure).
Add 1 grams of calcium carbonate to the mixture and continue
the grinding until t,he ingredients are thoroughly mixed (7 to 10
minutes). Place about 0.5 gram of calcium carbonate on the
bottom of a 40-ml. platinum crucible. add the mixture t o the
crucible, and compact the mixture with a muehroom glass rod.
Place about 0.5 gram of calcium carbonate in the mortar and
grind for about 2 minutes to rinse the mortar and pestle.
Distribute t,his calcium carbonate on the mixture in the crucible.
Mount the crucible through a hole in an asbestos board about 0.3
cm. thick, so bhat the rrucihle projects about 1 cm. above the
hoard. Cover the crucible with a well-fit,ting cover and set on i t
another platinum cruciiile or a 50-ml. beaker that is kept. filled