374 NOTES Vol.

64

algebraic manipulation of the relations appropriate Harned and Wrightll determined the normal
to the two cases, the error is shown to be only electrode potentid of the quinhydrone electrode
O.oooO1 p.p.ni. for CHC13, and should be equally from 0 to 40' by combining their data with activity
negligible for the other molecules studied. coefficients determined by Harned and Ehlers12
The most serious effect of bad resolution should by a different method.
be an increase in random errors, with the result In the present investigation the standard elec-
that the CL3effect would be rendered highly un- trode potentials of the quinhydrone electrode were
certain. If resolution varied substantially with measured from 25 to 55 a t 5" intervals, using a Ag-
sweep direction, :L directed error might be pro- AgCl reference electrode. The establishment of
duced; however, no evidence for such could be standard electrode potentials a t each interval allows
found by careful analysis of the data. The ap- the direct calculation of activity coefficients a t
parently poor resolution of the C13satellites for the these temperatures.
(CH3)& (as judged by the excess line width, In the calculations, it has been assumcd that the
ca. 0.12 c./sec., observed for them) is actually due cell reaction is
to the exceedingly weak spin-spin coupling between
protons on C13 and those on C12. This splitting
Quinone + 2HC1 + 2Ag r'Hydroquinone + 2'4gC1
becomes observable as a result of the "effective (1)
chemical shift," produced by the magnetic moment The electromotive force for this reaction is given
of individual C13 atoms upon their attached pro- by the Nernst equation in the forrr..
*
tons. The coupling constant, J(C12H3SiC13H3), E = EO,,II + RT
- In a m
F (2)
must be approx. 0.12 c./sec., the multiplet being
assumed to be 10-fold, with binomial intensity Since the quinhydrone used is an equimolar
distribution; J = (0.902- 0.782)i/2/3.6. compound of quinone and hydroquinone, and since
Acknowledgment.l-I am indebted to Donald these substances are non-electrolytes of low solu-
Hotchkiss for the excellent careful operation of the bility in contact with the solid, their activities
1i.s.r. equipment so nccessary in this work. should be constant. At higher temperatures, the
solubility of quinhydrone becomes appreciable
(7 g. per 100 g. Hz0),2but as long as the ratio of the
T H E S't'ANDARD ELECTRODE POTENTIAL activities of quinone and hydroquinone is nearly
OF THE QUINHYDRONE ELECTRODE constant, these activities may be ncglected. There-
FROM 225 to 55" fore, the Nernst equation may now be written
BY JoriN c. HAYES*AND M. H. LIETZKE 2RT
+
E = Eoc0i~ -F- In ~I~CIYHCI (3)
Contribalion f r o m the Chemistry Divisinn, Oak Ridoe National Lnborn-
toru. Oak Ridge, Tennessee If one assumes that
RPceived October 17, 1969
(4)
Since the discovery3 and development4 of the t5

quinhydrone ckctrode, it has found frequent use as

a substitute for the hydrogen electrode for pH where A and B are parameters and I = ionic
measurements. The electrode is convenient to use strength, S = 1.17202 (23375.2/DT)'/2,and D =
and it gives results which are easily reprodu~ible.~-~ dielectric constant of water (at temperature T ) ,
The earlier research established the fact that meas- determined by the Akerlof equation13then equation
urements with the electrode in certain solutions 3 may be rearranged to give
contained a "salt error,5 which was due* to a
change in the ratio of the activity of hydroquinone
and quinone caused by t,he presence of other dis- (5)
solved substances in solution. While other inves-
tigations werc concerned with the "salt-error," If the quantities on the right are equated to EO",
they also established the normal potential of the then
quinhydrone e l e ~ t r o d eas , ~well as the normal poten-
tials of t.hc hydroquinhydrone and the quinoquin-
hydrone electrodes.
The Eoat any one temperature may be determined
( 1 ) 1'111s paper is hasrd upon work performed for the Atomic Energy by extrapolating the Eo" values to zero ionic
Coinrnission at tlie Oak IWae National Laboratory operated by Union
Car'Gic. Coi jmration. strength. In this work, however, the parameters
(2) Reseal-sh I'a,rtiriiiant for the Sumnier, 1969, from IIainline A and B and the values of Eo in equation 5 were
Univi nlity. S t . I'aul. Alinnrsota. determined by a non-linear least squares method
(3) 1;. 1laht.r and R. Rims, Z . phvsik. Chrm.. 47, 257 (1904).
(4) S ( ; r a n g e - &nd .i. AI. Nelson, J . A m . Chem. Sor., 49, 1401
12.
on a high speed computer (the ORACLE).
( IR'L I J . Materials and Apparatus
(A) 15. 1riilcn:in. A n n . C h ? m . ,[9] 16. 109 (1921). Quinhydrone.-The quinhytironr n s r d in this projwt
( 6 ) .1. I,. It. Morgan, 0. h l . I,ainmert and hI. A . Campbell. J . A m . waa Enstman KO.217, rcrrystnllincd from wttcr hcntcd to
Cham. Soc.. 63. 454 (1931).
(7) E. Biilnran and .4. L. Jensen. Bull. soc. chrm.. 41, 151 (1027). (11) I[. S. Ilarncd anti D. D. Wright, J . A m . Chem. Soc., 66, ,4849
( 8 ) S. P. I,. Sijren,scn, AI. Sorensen and K. Iinderstrom-Lang, A n n . (1933).
Cham., 16, 283 (1!321). (12) H. 8. Harncd and R . W. Ehlcrs. J . A m . Chem. Soc., 66, 2179
(9) F. Ilovorka and W. C. nearing, J . A m . Chcm. Soc.. 67, 440 (1933~.
(1935). (13) G. C. Akcrlof and TI. 1. Oshry, J . A m . Chcm. Soc.. 79, 2844
( 1 0 ) 11. 1. Stonchill. T m n s Faradav Snc.. 39, F7 (1943). (1950).
March, 1960 NOTE s 375

65". Thc recrystallized product was dried overnight in :I TABLEI11

vaciiiim desiccator. The qiiinhydrone gave a melting point
:it 168 i 1'. ACTIVITYCOEFFICIENTS
OF HCl
Nitrogen. -All operations involving quinhydrone were 250
m 1" 212 3'6 4'4 5 I6 017
done in an at,mosphere of nitrogen. The biibbling of
nitrogen into the cell during e.m.f. measurements not only 0.001 0.9654 0 . !I656 0.9650 0.9653 0,9650
gave an incrt :itmosphere but also provided stirring of thc ,002 .!)524 ,9521 ,9520 ,9525 ,9519
solution. ,005 ,9287 .!I285 .9283 0.9284 ,9287 ,9280
Hydrochloric Acid.-Stock solutions of hydrochloric acid
were prepared from Fisher Certified Reagent Hydrochlorir .Ol ,9048 ,9048 ,9045 ,9044 ,8757 .(3040
Acid. Concentrations were determined by titration of the .02 ,8754 .8755 ,8753 ,8301 ,8747
solutions with standard alkali. Densities were determined .05 ,8295 ,8304 .BO8 ,8310 ,8310 .8296
by weighing a certain volume of solution. The concentra- .1 ,7923 ,7964 ,7967 ,7972 ,7938 .?'!I58
tions then were expressed in terms of molalities to eliminate
caorrections for thc change in volume a t different tempem- m 30'
tures. 0.001 0 !3652 0.9650 0.9648
Ag-AgC1 Electrodes.-The silver-silver chloride eler- ,002 ,9521 ,9515 ,9518
t rodes were prepared according to the method described by
Greeley.I4 ,005 ,9284 .9275 ,9274
Cell Measurements.-The cell potentials were measured .O1 ,9047 ,9034 ,9034
with a vibrating reed elect,rometer (Model 30, Applied .02 ,8759 ,8741 ,8741
Physics Corp.) used as a null instrument. Potentials wpre .05 ,8319 ,8285 ,8291
read from a potentiometer (type B, The Riibicon Co.) using a
Brown Recorder t o indicate equilibrium conditions. The cell .1 ,7981 ,7940 ,7946
was held in a constant temperature bath (controlled to m * 350
+0.02") by meanti of a brass tube holder which had holes 0,001 0.9648 0.9647
drilled in it to facilitate thermal eqiiilibriun. The tube holder
:dso shielded tbr. cell from any environmental capacitance. ,002 ,9515 ,9513
,005 ,9274 ,9268
Experimental
.01 .903S ,9025
The cells,, without the quinhydrone, were allowed to
equilibrate for a t least one hour in an atmosphere of NI. .02 ,8737 ,8731
Measurements of rlotential were started from 5 to 10 minutcs .05 .a279 ,8265
after the quinhydrone had been added. Eqiiilibriiim volt- .1 .7,9lG ,7918
:tges were considered constant when they did not change
rn 40"
more thnn 0.2 mv. in a half-hour period. Equilibrium volt-
nges oft,cn were olxerved within 15 minutes and rc,maincd 0.001 0 . !I642 0.0643 0.9642
r,ssent,i:dly constant for as long as 2 or 3 hoiirs. .002 ,9508 ,9505 .9507
Discussion of Results 005 ,9261 ,9265 ,9268
The EO valuers for the Ag -AgCl, quinhydrone cell .O1 ,9011 ,9016 ,9026
from 25 to 55'' are listed in Table I. The best .02 ,8701 ,8715 ,8735
value of the paramtter A in equation 4 was found .05 ,8208 ,8246, ,8283
to be 1.5. ,1 .77X ,7891 ,7927
m 450
1
T.4RLE
0.001 0.9F39 0.9644
THEAg-AgC1-&UINHYDRONE CELL ,002 ,9503 ,9504
250 300 350 400 450 550
,005 .!I253 ,9261
EO 0.4771 0 4702 0 4762 0.4765 0.4771 0.4770
(YB)" 0.0091i 0 0148 0.0120 0.0052 0.0062 0.0118
.01
02
,9001 .!loo8
,8090 ,8704
a This term is dcfincd i n cqiiation 5. .05 .8194 ,8232
1 ,5780 .7872
TABLE I1 m 550
STANDARD T'OTENTIALS OF
ELECTRODE QUINHTDRONE0,001 0.0GS1 0.9636
THE
ELECTRODE ,003 .94!)3 ,9497
250 300 350 400 450 550 005 .!I240 ,9240
0.6995" 0 6953 0.6919 0.0886 0.0854 0.6776 01 8987 ,8990
.G995* ,6953 .GO18 ,6885 ,6854 ,8776 02 ,8076 .8680
.699416 6952 ,8919 ,6885 ,6885 ,0776 .05 .8192 ,8195
699711 6!160 ,6923 ,0886 1 ,7801 ,7829
. G9948 " Ilcwilts of this investigation.

a Based on this investigation plus Eovaliies for Ag-AgC1

from Harned and Ehlers; see also h t c s "Electrometric pH The activity coefficients of hydrochloric acid are
Determinations, Theory and Practice," John Wiley and listed in Table 111. These values agree closely
Sons, Inc., New York, N. Y., 1954. Bascd on this in- with those obtained by other investigators. The
vcstigation plus ED values for Ag-AgC1 from Greelcy."
largest deviations occur a t 40 and 4 5 O , yet they are
The standard electrode potentials of the quin- still less than 1%. Agreement is unusually good
hydrone electrode have based based on the EO at the other temperatures. Hence it appears that
values of the Ag-AgC1 electrode from the values of the quinhydrone electrode may be used in activit,y
Harned and Eh.lers,I2 as well as those of GreeleyI* coefficient measurements in a manner similar to the
(which were measured in this Laboratory). As hydrogen electrode.
shown in Table 11, these values agree usually to
within 0.1 mv. (15) R. G Bates and V. E. Bower, J . liesearch N d l . Bur. Standnrds.
63,283 (1951).
(14) R. S. Greeley, Ph.D. Thesis, University of Tennessee, May 22, (16) T . Shedlovsky, .I. A m . Chem. Soc., 79, 3680 (1950).
1959. (17) G . J. IIllla and D. J. G. Ives, J . Chem. Soc., 318 (1951).
376 h70TES Vol. 64
Acknowledgment.-The authors wish to thank I11
TABLE
Dr. R. W. Stoughton for intcrcsting discussions in HEATSOF SOIJJTIONO F IiClO,,(e)
connection with this work. nroirs IKX)~ x 103/
950 1111. IT20 A?l(kcnl./molr)
4.245 9.87
THERMOCHEMISTRY OF POTASSIUM 6.822 9.92
PERMYANGANATE, POTASSIUM 7 . 770 9.85
MOLYBDATE, POTASSIUM C,HLORATE, 11.01 9.90
SODIlJM CHLORATE, SODIUM 12.93 9.91
16.16 9.90
CHROMATE AND SODIUM DICHROMATE
BYTHOMAS Moss AND LORENG. HEPLER~
NELSON, CALVIN TABLE IV
Contribution from Cobb Chemirnl Lnborntorg. UniversifQ o f Virgiiiia HEATSOF Sor.r~i,ro~
OF KaC103(c)
Charluttuuille. Va. Molrs NaCIO. X 102,'
Received October 66,1969 9.50 nd. 1lzO Al€(Rcnl./mole~
5.21 0.9260
Heats of ,solut?ion of KMn04(c), KCIOa(c),
5.21 1 ,032
NaC103(c) and NnnCr04(c) and the heat of re-
5.23 1 .OF2
action of Na26r207(c) with excess OH-(aq) have
5.23 1,178
been determimd as part of an undergraduate re-
5.24 I .263
search program. These heats have been used for
5.24 2.270
calculation of standard heats of formation of
K2M004(c),Na2CrO4(c)and NazCrzOi(c)and stand-
ard partial rrtolal entropies of Mn04-(aq) and TABLEV
ClOa-(aq). HEATSOF SOLUTION
O F Nn2Cr04(c) IN l o w 3.If OH-(aq)
Rlolrs NaCrOd x lo'/
Experimental 950 nil. soln. AH(konl./mole)
The solution calorimeter used for these determinations 0,5632 -4.42
has been described.*-* All calorimetric determinations
were carried out at 25.0 f 0.2' with 050 ml. of water or ,6645 -4.44
solution in the calorimeter. .979 1 -4.42
All of the saltis were prepared for use in the calorimeter 1.016 -4.3!)
by recrystallization of the appropriate reagents and all ex- 1,137 -4.43
cept NaC1O8 and KCIO, were analyzed by common volu-
metric methods. Some samples were dried in vacuum de- 1.408 -4.36
siccators and some in an air oven.
Heats of reaction of Nx2Crz07(c)with a small
Results excess of aqueous NaOII as in the equation
Heats of solution of KMn04(c), K2Mo04(c), Na2Cr207(c)+ 2OH-(aq) = 2Nn+(aq) + 2Cr04'(nq) +
KC103(c), NaClOl(c) and Na2Cr04(c)are given in N20(1) ( 2 )
Tables I-V. I n each table, AH refcrs to the re-
action are given in Table 1'1.
salt(c) = snlt(nq) (1) T A B L E VI

TABLE
I HEATSO F SOLUTION
O F K:&r207(r) IN OH-(nq)
RTolrs NnrCrKh X 1 0 3 /
HEATS OF SOLUTION O F KMn04(c) 950 nll. s d n . AI(il?s 011- X IO2 Alf(kcnl.,'~nole)
hloles IZMnOl X lo*/
950 nil. HrO A€l(kcal./molr) 2.087 1 .0 -21.36
4.810 10.42 2.646 1.0 -21 .:14
5.G87 10.30 4.302 1.5 -21.33
6. 345 10.43 4.640 1.5 -21.49
6.5i0 10.44 5.106 2.0 -21.36
7.187 10.42 6.549 1.5 -21.23
9 !I I58 10.44 6.567 1.8 -21.32
8.566 2 .5 -21.34
TABLEI1 10.482 2.5 -21 26
~ I E A TOF~ SOLUTION
OF K2MoOr(c) IN 10-8 A4 OH-(aq)
Mole8 KrR'loOi X loz/ Heats of dilution of I<C10.1(aq) and XaC103 have
950 nil. s d n . A??(kcnl./mole) been taken from National Bureau of Standards
0.5741 -0.82 Circular 5006 and heats of dilution of KMn04(aq),
1.100 - .79 KzMoOr(aq) and NaZCrO4(aq)have been estimated
1.359 - .82 from heats of dilution5 of KC104(aq), K2S04(aq)
1 . ti23 - .79 and NaB04(aq), respectively. Standard heats of
1 ,746 - .75 solution calculated from these heats of dilut,ion and
I .784 - .i7 data in Tables I-Tr are given in Table VII. The
2 . o"2 - .73 standard heat of reaction which is also given in
Table VI1 is based on the data in Table VI and
( 1 ) Alfred P. Sloan Foundation Research Fellow. estimated heats of dilution. Our estimates of
( 2 ) R. L. Gruhain and L. G . Ilepler, J . Ani. Chem. Sor., 7 8 . 48.16
(1956).
total maximum uncertainties are indicated by f.
('0 (.. N. RIiilrIrox, .Jr., and L. Q. Ilrpler, ihid. 79, 4045 (195;). ( 5 ) "Selccted Values of Chrrnical Thermodynamic Protwrt ies,"
( 4 ) 3 f . R I R i r k y and L. C . llepier, to hr ~ ~ i ~ h l i s h e d . Cirrulnr 500, National Hiireau of Stnndnr,ls, 1052.