THE ACIDITY CONSTANT OF THE HYDROGEN CHROMATE ION IN THE RANGE 5-60" IN WATER

By H , G. LINGE*and A. L. JONES*
[Manuscriptreceived March 20, 19681 Summary
The equilibrium HCr0; + Cr0;-+H+ in water has been studied by potentiometric and independent spectrophotometric methods between 5' and GO0. The thermodynamic quantities AS0, AHa, and AC, have been evaluated.

Although the acidity constant, K,, of the hydrogen chromate ion has been studied by a number of workersl-4 at 25" and the heat of the reaction a t 25" is known,5 there has been no direct study of this equilibrium at other temperatures. Estimation of acidity constants at other temperatures from a single K , value and the heat of reaction at only one temperature can lead to serious errors since the dependence of logK, upon T-l is usually not linear.'j Since our work on the dissolution of silver chromate crystals into aqueous solutions has required values of K, over a range of temperatures, we have determined this quantity in the range 5-60" by a potentiometric method, and in the range 1 5 4 5 ' by independent spectrophotometric measurements, the results being reported in this paper.

Dried A.R. chemicals and deionized water were used throughout. Stock solutions of weighed quantities of potassium chromate were made up using freshly boiled, deionized water. They were cooled under nitrogen and protected against atmospheric carbon dioxide. The stock perchloric acid was prepared similarly from the A.R. acid and assayed by titration against sodium hydroxide which had previously been standardized against potassium hydrogen perchloric phthalate. Standard solutions of potassium dichromate were made up in 2 x 1 0 - 3 ~ acid, to minimize chromate ion formation. The standardizing tartrate, phthalate, phosphate, and borate buffers were prepared according to the recommendations of Bates.' The titration equipment was essentially as described by Albert and Serjeant.8 Additions of C0,-free

* Department

of Chemistry, Monash University, Clayton, Vic. 3168. Neuss, J. D., and Rieman, W., J. Am. chem. Soc., 1934, 56, 2238. Howard, J. R., Nair, V. S. K., and Nancollas, G. H., Trans. Paraday Soc., 1958, 54, 1034. Bailey, N., Carrington, A,, Lott, K. A. K., and Symons, M. C. R., J. chem. Soc., 1960, 290. Sasaki, Y., Acta chem. scand., 1962, 16, 719. Hepler, L. G., J. Am. chem. Soc., 1958, 80, 6181. Bell, R. P., "The Proton in Chemistry." (Methuen: London 1959.) Bates, R. G., "Determination of pH." (John Wiley: New York 1965.) Albert, A., and Serjeant, E. P., "Ionization Constants of Acids and Bases." (Methuen: London 1962.)

Aust. J . Chem., 1968, 21, 2189-98

2190

H. G. LINGE AND A. L. JONES

acid to the C0,-free potassium chromate solution were made dropwise from a standardized burette of 5-ml capacity. Titrant volumes could be determined to 0.01 ml, concentrations being arranged so that the ratio [c~o:-]/(total [CrVr]) was varied a t least between 0.7, and 0.2,. The solution was kept free of CO, during the titration by maintaining a stream of oxygen-free nitrogen saturated with water vapour a t the experimental temperature. The nitrogen flow was started about 15 min before beginning the titration, the solution being stirred by a n efficient glass stirrer. This time was sufficient to remove any atmospheric CO, absorbed by the potassium chromate during the transfer from the storage vessel into the cell, as was indicated by blank experiments with water. Mixing during the titration was provided by the nitrogen bubbling through the solution, this being stopped during the pH measurements, which otherwise were found to be affected. pH measurements were made with a Radiometer pHM4 meter in the range 5-45' and with a Radiometer pHM22 meter, fitted with a n automatic temperature compensator, a t 60". Throughout the work a Radiometer G202C glass and K401 calomel electrode were used. The performance of these electrodes was checked over the entire pH scale before commencing the work and with a t least two different buffers before and after each experiment. The relevant standard N.B.S. p H values for the different buffers mere those of Bates7 and the internal agreement found a t all temperatures with the above electrodes was generally to k 0 . 0 1 pH unit or better. Drifts in buffer adjustment settings of the instruments during the experiments were always less than 1 0 . 0 2 p H units. TABLE1
LIQUID JUNCTION EFFECTS I N PROSPHATE BUFFERS AT

20'0

Concn. (mole 1.-l) 0.025 0.0025 0.001 0.0001

PH Calc.&
6.88 7.08 7.14 5.20

APE PH C a l ~ . ~ ExpectedC
Od 0.01 0.02 0.04 6.88 7.09 7.16 7.24

PH Observed 6-88*0.01 7.0810.02 7.12+0.02 7.25*0.05

" Calculated from available data.'

O

Calculated from the Henderson equation7 and available mobilities.9 pH(expected) = pH(calcu1ated) $- ApH. Used as primary buffer for standardizing the instrument.

Check experiments to determine liquid junction effects on measured p H values were carried out a t 20' using a series of C0,-free phosphate buffers, their expected p H values being calculated from available data.7.9 Table 1 summarizes the results, showing increased irreproducibilities with increasing dilution and a n overcorrection of results by the Henderson equation in the more concentrated solutions. Assuming a similar behaviour in potassium chromate solutions, all work was carried out in the concentration range 0.001-0.006x, no corrections to measured pH values being applied for any change in junction potential, and therefore the instrument buffer setting, on changing the test solution. A general irreproducibility of about h 0 . 0 2 pH units was expected therefore, this being due possibly to lack of sufficient cylindrical symmetry10 in the porous plug junction of the K401 calomel electrode. Contamination of the test solution by potassium chloride from the reference electrode amounted to about 2 x l o d B moles as judged from test conductance experiments with water.
9

lo

Landolt-Bornstein, "Tabellen." 6th Edn, Vol. 11, Part 7. (Springer-Verlag: Berlin 1960.) Guggenheim, E. A., J. Am. chem. Soc., 1930, 52, 1315.

THE EQUILIBRIUM HCrOh

+ cr0:-

+H+

2191

Errors resulting in the ionic strength by neglecting this concentration term (2x 10-5 mole I.-=) were thus negligible. Optical densities were measured with a Shimadzu QR50 spectrophotometer.' No significant variation could be detected in the measured molar extinction coefficient of alkaline potassium chromate over a range of optical densities a t several wavelengths. Handling of the pairs of 1-mm and 1-cm stoppered suprasil cells used was reduced to a minimum, all solutions being transferred, when necessary under nitrogen, by syringe pipettes. The temperature of the cell compartment was controlled by circulating thermostatted water. Test experiments with a chromel-alumel thermocouple, either on the solution to be measured or, where this was to be protected from atmospheric CO,, on an identical solution in a third spectral cell inside the cell compartment, showed that after a n equilibration period of 10-15 min the temperature remained steady a t the required value h0.2'. The titration apparatus where was placed inside a thermostatted bath with temperature control of &O.lD,except a t jO, this was 10.5'. Concentration corrections due to heating or cooling solutions prepared a t room temperature were carried out using tabulated values of the density of water.ll

The most important pH-determining and light-absorbing species in potassium chromate-perchloric acid mixtures are Cr0:-, HCrO;, and Cr,O;-. The equilibrium constant for Cr,O:-+2H20 + 2HCrO; is 0.03 a t 25012 and the acidity constant of HCrO, is about 3 x10-' at 25'., Therefore in our strongest solutions, where , the pH is 6 then [CrO!-] 1 : 1.2 x 1 0 - 3 ~ [HCrO;] , E total [CrV1]E 6 - 5x 1 0 - 3 ~ if 4.1 x lo-%, and [Cr,O:-] E 6 x 1 0 - 4 ~ In . contrast using the approximate value of unity13 for the dissociation constants of both H2Cr04+ HCrO;+Hf and HCr,O; + Cr,O;-+H+, we estimate that [HCr,O;] r! 6 x 10-1~and [H,CrO,] 2 4 x 1 0 - 9 ~ . Similarly, when pH = 7, then [CrOf ] E 4.8 x lo-%, [HCrO;] E 1-6 x 1 0 - 3 ~and , [Cr,O;-] 1 : 8 x 10-5~, and the estimated [HCr,O;] and [H,Cr04] are again negligible a t 8 x 10-lk and 2 x lo-% respectively. The value 0.3 has been estimated14 for the thermodynamic dissociation constant of the ion pair KCrO;, the concentration then being of this species in our strongest solution of ionic strength I < 0 . 0 2 ~ approximately 8 x 1 0 - 5 ~ .Since no allowance was made for the presence of HCrO; in the estimation of this constant, we believe 8 x 1 0 - 6 ~to be an overestimate for [KCrO;]. This view is supported by the constancy of the observed molar extinction coefficient of alkaline potassium chromate in the range 10-"3 x 1 0 - 3 ~ a t wavelengths of 260-404 mp, typical results being illustrated in Figure 2 below. No equilibrium data are available for the species KCr,O; but its concentration will not be significant a t these low values of [Cr,O;-1. Similarly no ion pairs between singly charged species are considered. These usually have dissociation constants in excess of unity and thus will be present in the above solutions only a t negligible concentrations.
"Handbook of Chemistry and Physics" 41st Edn. (Chemical Rubber Publishing Co.: Cleveland, Ohio, 1960.) l2Linge, H. C., and Jones, A. L., Aust. J . Chem., 1968, 21, 1445. l 8 Tong, J. Y., and King, E. L., 3. Am. ohem. Soc., 1953, 75, 6180. l4Banks, W.H., Righellato, E. C., and Davies, C. W., Trans. Paraday Soo., 1931, 27, 621.

2192

H. G. LINGE AND A. L. JONES

The thermodynamic acidity constant of the hydrogen-chromate ion K,, is defined by

where f, is the activity coefficient of an ion of charge z and {H+), the activity of H+, is related to the measured pH by

The concentrations of CrOi-, HCrO;, and Cr,Ot- are related by mass balance, electroneutrality, and the equilibrium expression

and reduce to:

[HCrOJ where R
= 4K-lf

= R-l[{2R(m-[CrO:-1)

+l)a -11

:f il; m = total [CrV1]; P = total perchloric acid concentration.

(6)

Values of K12 and K,,16 the ionic product of water, are available in the required temperature range. Although the Davies equation16 -log f, = ax2 (I*(l+It)-1-bI) is probably the most accurate relationship for reproducing ionic activity coefficients in concentrated solutions, its use is limited since the empirical parameters a and b are only known at 25". At each temperature values of f, were thus obtained from the Giintelberg relationship1' values of the constant A at each temperature being available.18 Values off, ( z < 2) obtained from (7) differ by less than 2% in our most concentrated solutions, from those obtained by the Davies equation. The uncertainty in K, so produced is insignificant compared to that arising from irreproducibilities of 1 0 . 0 2 units in the pH measurements. The expression for the ionic strength reduces to

A computer was used to evaluate [HCrOJ and [CrOi-] from the known experimental quantities m, P, and pH and equations (2)-(7) by successive approximation, starting with [Cr20;-] = 0 in equation (8), until the ionic strength showed a convergency of 1%. Prom these, values of K , were derived. Table 2 shows the results of one experiment at 35", listing ionic concentrations and derived values of K,, together with the mean.
15

16

Harned, H. S., and Hamer, W. J., J. Am. chem. Soc., 1933, 55, 2194. Davies, C . W., "Ion Assooiation." (Butterworths: London 1962.) 17 Giintelberg, E., 2. phys. Chem., 1926, 123, 243. 18 Manov, G. G., Bates, R. G., Hamer, W. J., and Aoree, S. F., J. Am. chem. Soc., 1943, 65, 1766.

THE EQUILIBRIUM HCr04

+ ~i-0:- + H +

2193

Table 3 shows a summary of the results obtained in the range 5-60". At each temperature except 60, a t least two experiments were carried out and a t 25", 35", and 45" these involved two independent stock solutions of potassium chromate. Also recorded are the mean values of K , a t each temperature.
TABLE 2 K, AT 35' FROM POTENTIOMETRIC DATA Experiment A2. rn, P, I, K,, [Cr40;-], and [HCrO;] in mole 1.-I
T H E ACIDITY CONSTANT

10Sm

pH

lo4p

1081

104[~r,0:-]

104[HCr0;]

lO7K,

Mean 107K, = 2.9,. TABLE 3

SUMXARY OF VALUES

OF

K,

IN

THE

RANGE

5-80'

OBTAINED

BY

THE

P O T E N T I O X E T R I C METHOD

Experiments prefixed B were a t a total [CrV1]six times greater than those prefixed A, the latter concentration being similar to those listed in Table 2. K, in mole 1.-I Temp. Expt. 107Kaa Mean 107K,"

60
a

B4

2.2,

2.2,&0.2

Mean Value for each experiment. Mean Value of all data a t that temperature.

At every wavelength, the optical density D of 1-cm thickness of potassium chromate-perchloric acid mixture will be given by

2194

H. G. LINGE AND A. L. JONES

where E, are the respective molar extinction coefficients assumed to be independent of the ionic strength of the solution.13

Fig. 2

ci

Fig. - 1.-Observed molar extinction coefficient E of acidified potassium dichromate solutions Series 1; A,series 2. At 25', K 2.9, X plotted against computed values of a (eqn. (10)). 0, (in eqn. (3)). Graph 1 : A 260 mp Graph 2: 360 Graph 3: 390 10-'cl 21, 143 52.,
'

Fig. 2.-Observed molar extinction ooefficient E, of alkaline potassium chromate solutions plotted against [CrOj-1. Series 1 (0, 1-om; 1-mm optical cells used): values are the average of two independent determinations on samples prepared from the same stock solutions, except a t 15" where only one determination was made. Series 2 (+, 1-cm; A, 1-mm cells) : single determinations on samples from an independent stock solution. Graph Graph Graph Graph
1: temp. 15'

lo-%, 65.,, 38., 33.,

A 260 mp
380 373 404

2: 3: 4:

25 35 45

10-l~ 31, ~ 27, 47, 142

Values of el and e, a t the required wavelengths were obtained from measurements of the optical density of acidified potassium dichromate solutions these being done a t 25" only, since these constants do not depend on temperature in the range 15-45".12 The data, obtained from two independent series of solutions prepared from different potassium dichromate stocks, were analysed using the method and result a t 25" of the previous work.l2 Figure 1 shows some typical plots, a t a number of

THE EQUILIBRIUM HCr0;

+-cr0;-

+H+

2195

wavelengths, of the apparent molar extinction coefficient of CrV1, E , against a, the fraction of CrV1in the form of Cr20:-, these quantities being related by12
E

=E ~ + ( O - ~ E ~ - E ~ ) ~

(10)

Values of E, a t the required wavelengths were obtained from optical density measurements on alkaline potassium chromate solutions between 15" and 45". These values showed no significant variation with [CrOi-] in the range 10-"3 X 1 0 - 3 ~ and some typical plots are shown in Figure 2. Between 15" and 45" the temperature dependence of E, can be represented within the experimental error, about &l%, by the linear equation E: = et5-k(t-25), where tOcis the temperature. The values found for the constants 6;' and E are summarized in Table 4, which also lists our data for comparison. The values of 6, and E, together with literature2~3,12*l3~19920 agreement obtained is satisfactory.
TABLE4
el
OF HCrO;, cr,~:, ,are independent of temperature in the range 15-45'. eca - a 25 -k(t-25)
MOLAR EXTINOTION COEFFICIENTS

AND
e 5 :

and

e,

~r0f and Ic are related by

Ref.

,
260 270 280 350

Wavelength (mp)
355 360 365 373 380 390 404

1
a

Present work.

For the potassium chromateperchloric acid mixtures we let rn' be the molarity of CrV1existing as HCrO, and Cr20;-;
rn = [CrO:-] +m'
I9
20

(11)

Davies, W. G., and Prue, J. E., T ~ a n s Faraday . Soc., 1955, 51, 1045. Vandenbelt, J. M., Forsyth, J., and Garnet, A., I n d . Emgng Chem. analyt. E d n , 1945, 17, 235.

2196

H. G. LINGE AND A. L. JONES

The effective molar extinction coefficient, e, for these two ions is given by equation (lo), in which the fraction a is now: a = 1-[HCrOJ/mt Solution of equations (9), (lo), and (11) yields: [Grot-] = (D-me)(,
-)-I

(12)

(13) (14)

m' = (me,-D)(e,-e)-1 I n terms of the above symbols, the ionic strength reduces to

I = 3m+O -5m'(a-2) +[H+]

(15)

Similar to the method of Howard et a1.,2 the expression for the acidity constant (1) is rewritten as

Y = K,{H+)-1X
where, using equation (7) also,

(16)

= (1-a)-1[D-m{el+(O~5e,-el)a)]exp{-6

.909AI*(l+I*)-l)

(17)

and contains most of the experimental error, while

Fig. 3.-Plot of Y against X for the results a t 35'. Numbers are wavelengths in mp. See Table 5 for details of experiments 1, 2, and 3.

A computer was used t o evaluate values of Y and X at every wavelength by successive approximation of both a and m'. First, with a put equal to zero, equation (14) provided a value of rn' which then was used to solve equations (12), (6), and (7) for a by successive approximation of the ionic strength through equation (15). This value of a was then used to obtain a next value of m' from equation (14), the cycles being repeated until both rn' and a were convergent t o 0.2%. Data were recorded a t 11wavelengths in the interval 260-404 mp, where the relative absorbances of HCrO;, CrOf-, and Cr,Ot- are such that the clustering of experimental points in the plots of Y against X is a minimum. Figure 3 shows these plots for the results a t 35". The values of K , derived from the slopes and the measured pH of the

THE EQUILIBRIUM HCrOa

+ ~ r 0 : - +H+

2197

corresponding solutions are listed in Table 5 . The good linearity of these plots obtained from data covering a fair region of the visible spectrum of respectively HCrO,, CrOi-, and Cr,Oi-, confirms the absence from our solutions of significant amounts of entities not considered in the present analysis.
K, TABLE5 35' F R O M

THE ACIDITY

CONSTANT

AT

THE SPECTROPHOTOMETRIO

DATA SHOWN I N FIGURE

3 3 6.73 1.6, 3.0,

Experiment PH Slopea ~o'K,~

a

1 6.04 0.32, 2.Q1

2 6.29 0.55, 2.8,

Slope of the plots of Y against X shown in Figure 3. Calculated from the slope by equation (16). TABLE6

K, IN THE RANGE 15-45' The K, values are the calculated mean from all spectrophotometric results a t each temperature
SUMMARY OR OBTAINED VALUES OF

Temperature No. of experimentsa 1 0 ' ~ ~

15' 3 3.3,*0.1

25" 9 3.l6j=0.0,

3 5 O 3 2.9,f 0 . 1

4 5 O 7 2.5,f 0.1

a Number of experiments on independent solutions containing the same total amount of CrV1but having different values for [C~O;-]/(total [CrV1]).

The mean values of K, at 15-45', obtained by the spectrophotometric method are summarized in Table 6, the agreement with values obtained by the potentiometric method being within the limits expected for an uncertainty of 1 0 . 0 2 units in pH measurement.

-6.45

-6'50

Fig. 4.-Variation of logK, with T-I. 0 Potentiometrio, present work; [7 spectrophotometric, present work; ref. 3; A ref. 2; ref. 1.

The plot of logK, against T-l, which also shows the good agreement with literature values of K, a t 25",is shown in Figure 4. From this we derive the variation

2198

H. G. LINGE AND A. L. JONES

with temperature of the heat of the reaction, AH:, reaction, A S ! , as:

and the change in entropy of

giving also AC,, the change of heat capacity of the system: AC,
= 3,f

lo cal mole-1

this latter value being independent of temperature within the accuracy of the present data. The only other values of these quantities that appear in the literature are those of Hepler6 who obtained AH:,, = -0.7&0.4 kcal mole-I from calorimetric measurements and calculated AS:,, = -32.1 e.u. using the value for K , a t 25' obtained by Neuss and Riemann.l Values of ACp for this system do not appear in the literature, but our result is similar to values tabulated6 for a variety of acid equilibria in water.

The authors thank Broken Hill Proprietary Company Ltd for the award to one of us (H.G.L.) of a postgraduate research scholarship.