A. FOJTIK, G. CZAPSKI,AND A. HENGLEIN
3204
Pulse Radiolytic Investigation of the Carboxyl Radical in Aqueous Solution by A. Fojtik,la G. Czapski,lband A. Henglein Hahn-Meitner-lnstitut far Kernjorschung Berlin, Sektor Strahlenchemie, Berlin-wannsee, Germany (Received March 26, 1970)
Optical absorption and electrical conductivity measurements were performed simultaneously to study the intermediates in the pulse radiolysis of aqueous solutions of carbon monoxide and formic acid. CO- which is formed by the addition of the hydrated electron to CO absorbs at 2600 A with e (1200 f 200) M-’ cm-1. It is rapidly protonated. The carboxyl radical is formed in the oxidation of CO by OH. Its p K value is 3.9 f 0.3, and its molar conductivity 63 -i: 4 ohm-’ cm2mol-’. The same pK and molar conductivity were found for the oxidation product of formic acid. COZ- and COOH both reduce nitrobenzene with rate constants of (1.0 f 0.2) X IO9 iM-’sec-l and (5.6 i 1) X lo82M-’ sec-’, respectively. COz- transfers its electron to 02.
Introduction The y radiolysis of aqueous formic acid solutions has often been The main products besides H, are oxalic acid and carbon dioxide, and the relative yields depend on the pH. The carboxyl radical has been postulated as an important intermediate and may exist in an acidic and a basic form COOH J_ C02-
+ H+
(1)
Pulse radiolytic studies of formic acid solutions gave information about the absorption spectrum and the second-order rate constant of the disappearance of this radicaL6 At pH 5 , a positive kinetic salt effect on this rate constant was found, showing that the carboxyl radical exists in its basic form at this pH. I n the oxidation of CO by the OH radical, a species having the same absorption and rate of disappearance has been observed. The pK of the carboxyl radical has not yet been satisfactorily measured. Optical absorption measurements in pulse radiolysis are useful to determine pK values only if the acid and the basic form of a pa,rticle have sufficiently different absorptions. It has earlier been shown that this must not always be the case.6 For example, half-reduced diacetyl has practically the same absorption spectrum in the acid and basic form.6 The simultaneous measurement of the electrical conductivity after the pulse often gives useful additional information. I n the present study, aqueous CO and formic acid solutions were pulse irradiated and the optical absorption and electrical conductivity were simultaneously recorded as a function of time. Experimental Section The pulse equipment of the Hahn-Rleitner-Institut at Berlin has already been described (Van de Graaff generator; 1.6-hlIeV electrons; 10 mA-beam currrent; The Journal of Physical Chemistry, Val. 74, N o . 17,1970
pulse length variable from 0.5 to 50 psec; dose equal to 700 rads per psec of p u l ~ e ) . ~The , ~ cell for the optical measurements contained two platinum electrodes for the conductivity measurements. A potential of 20 V was applied to the electrodes over a 1-kilohm resistor. Only a small part of the ions was discharged at the electrodes. The voltage drop across the resistor which was recorded as function of time is therefore proportional to the actual concentration of charged particles. From the observed signal the change in molar conductivity can be calculated from the absorbed dose and G value of all conducting species. Conductivity was traced as a function of time before and after the pulse. No meaningful signal could be obtained during the pulse. Doses were determined by filling the cell with aerated aqueous thiocyanate or tetranitromethane solutions in which strongly absorbing species with known extinction coefficients and yields are produced by the pulse. [(CNS)t- absorbing at 4750 A with E = 7.1 X los M-l cm-l is formed with G = 2.3;9,10 C(NO&- absorbing (1) (a) Czechoslovak Academy of Science, Praha, Institute of Physical Chemistry; (b) Hebrew University, Jeruaalern, Department of Chemistry. (2) (a) H. Fricke, E. J. Hart, and H. I?. Smith, J. Chem. Phys., 6 , 229 (1938); (b) T.J. Hardwick, Radiat. Res., 12, 5 (1960). (3) E. J. Hart, J . Amer. Chem. Sac., 83, 567 (1961). (4) E. J , Hart, J. K. Thomas, and S. Gordon, Radiat. Res. Suppl., 4, 74 (1964). ( 5 ) J. P. Keene, J. Raef, and A. J. Swallow in “Pulse Radiolysis,” M. Ebert, J. P. Keene, A. J. Swallow, and J. H. Baxendale, Ed., Academic Press, New York, N. Y . , 1965, p 99. (6) J. Lilie and A. Henglein, Ber. Bunsenges. Phys. Chem., 72, 549 (1968). (7) G. Beck, Int. J . Rad. Phys. Chem., 1, 361 (1969). (8) A. Henglein, W. Schnabel, and J. Wendenburg, “Einftlhrung in die Strahlenchemie,” Verlag Chomie, Weinheim, 1969. (9) G. E. Adams, J. W. Boag, J. Currant, and B. D. Michael, in ‘’Pulse Radiolysis,” ref 5, p 131. (10) J. H. Baxendale, P . L. T. Bevan, and B. A. Scott, Trans. Faraday SOC.,64, 2389 (1968).
PULSE
RAnIoLYTIc INVESTIGATION OF THE CARBOXn RAnIcAL
a t 3 5 0 0 i with t 1.5 X lo' M-l cm-' is produced with G = 3.3.'l] The conductivity induced in tetranitromethane solutions was used to calibrate the cell. The procedure has previously been described in detail.' Each pulse was also monitored by a secondary emission chamber placed in the beam before the cell. Carbon monoxide and nitrous oxide were carefully purified by bubbling the gases through two flasks containing alkaline pyrogallol, one flask filled with a warmed acid CrII solution and finally through one flask containing pure water.
3205
clrnsFigure 1. Change in conductivity and 2 6 0 0 - ~absorption of a CO-saturated aqueous solution as a function of time at pH 3.7; initial total radical concentration 5 X 10- M .
PH
n-I
Results and Discussion CO-Saturated A p o u s Solutions. Carbon monoxide dissolves in water in sufficiently high concentration (1 X lo-' M a t 20') to scavenge all OH radicals and hydrated electrons. ea*- reacts with k = 1.0 X los M-I sec-l and OH with k = 6 X lo8 M-' sec-I. The reactions with CO occur during the pulse or within a few microseconds after the pulse. Figure 1 shows the conductivity and optical absorption changes as a function of time. The solution was saturated with CO; the pH was 3.7. Assuming that both eaq- and OH form radicals in their reactions with CO and using a G value of 5.5/100 eV, one calculates an M a t the initial total radical concentration of 5 X applied absorbed dose of 880 rads. Immediately after the pulse, the conductivity and the optical absorption a t 2600 A are increased. The rate of subsequent decrease in both cases is faster at higher doses which indicates second-order disappearance of the intermediates. The optical absorption curve did not show significant changes in the pH range investigated from 3 to 8. The conductivity curve, however, varied strongly. I n order to investigate the conductivity change shortly after the pulse, photographs were taken a t a faster time sweep of the oscillograph. The dose in the pulse was lowered to 90 rads, giving an initial total concentration of intermediates of only 5 X M. Under these conditions, the pH of the solution was not drastically changed by the protons generated in the pulse. Figure 2a-d shows oscillograms a t various pH values. It can be seen that the positive signal at pH 7.8 drops within about 15 psec to reach finally a negative value. At pH 6.3, the drop is less pronounced and the signal remains positive. It decreases after much longer times (not shown in Figure 2b). At pH 4.5, an initial drop is absent and finally at pH 3.5 a weak positive signal is observed. Both the hydrated electron and the OH radical may lead to conducting species in their reactions with CO ea,,-
+ CO
CO-
+ H + +HCO
followed by
-P
CO-
(2)
(3)
70 6.3 L.5
3.5
tlOOpS-, Figure 2. (a-dj Change in conductivity ss a function of time at various pH values; initial total radical concentration 5 X 10-7 M; (e) change in eonduct,ivity as a function of pH in the presence of 2-propanol (0.1 Mj. Initial total radical concentration 2.5 X 10- M. The ordinate scale is different from t,he upper curves (a-d).
followed by COOH -+ Cot-
OH
+ CO +COOH
(5)
Figure 2e shows the conductivity as function of time in a CO saturated solution which contained lo-' M 2-propanol. The OH radical is scavenged here by the alcohol. The conductivity change can now only he produced by the CO- radicals formed in reaction 2 (and the same number of protons formed in the pulse). The initial conductivity increase drops to zero with a first half time of 10 psec. Since the initial CO- and H + concentrations were 2.5 X 10-6 M in this experiment, the rate constant of the reaction responsible for the X 10-5 = 4 X 1O'O M-' sec-I drop is 1/25 X which is of the order of a neutralization process. At lower pH values, the drop was much faster. Zero conductivity change was always attained after the drop. We explain this result by the fast disappearance of CO- and H f after the pulse according to eq 3. A (11) K.-D. Asrnus and A. Henglein. Be?. Bunsenges. Phys. C h m . . 68,
and
+ Hf
348 (1964).
(12) M. Anbar and R. Net& Int. J . A p p l . Rad. Isotopes. 18, 493
(4)
(1967). The Jouiml of Physical Chemistry. Vol. 74,No. 17, 1970
A. FOJTIK, G. CZAPSKI, AND A. HENGLEIN
3206
PH
-
Figure 3. Change in conductivity 30 ps after the pulse vs. pH (CO saturated solution. Ordinate: deflection on the oscilloscope in mV which is proportional to the conductivity change. Initial radical concentration: 5 X lo-’ M . Measurements below pH 3.5 were not possible because of the high “background conductivity” of the solution).
few experiments were also carried out with alkaline solutions of pH 200. It can therefore be assumed that OH radicals are formed with G = G(0H) +G(e,,-) = 5.5/100 eV and these react with CO according to eq 4. By comparing the measured optical density with the absorbed dose determined as described in the Experimental Section an extinction coefficient of
+
+
~ ~ 0 ~ - ( 2 A) 6 0 0= 2200 M-’ cm-1 was calculated. Keene, et al., found 2250 M-‘ cm-’ at 2500 A.5 The extinction coefficient of CO- can be determined by comparing the initial optical densities O D N , and ~ ODco of solutions containing the N20/C0 mixture of pure CO, respectively. The ratio of these two optical densities should be equal to
A ratio of 1.3 was found at 2600 A. Knowing rcoe- = 2200 M - I cm-’, G(e,,-) = 2.7 and G(0H) = 2.8, ECO- a t 2600 A could be calculated as 1200 M-l cm-I. This value is uncertain by =kt00 M-’ cm-l, if one takes into account the H atoms which are formed in the radiolysis of water. The percentages of the H atoms that react with NzO or CO are not known. The secondorder decay of the optical absorption and conductivity at longer times after the pulse (Figure 1) is probably not characteristic of a single reaction, since HCO and C02- are both present and may either combine mutually or among themselves. I n the case of the NzO/CO mixture mentioned above, the absorption also decayed by a second-order process. In this case the carboxyl radical is the only significant species. Evaluation of both the optical absorption and conductivity measurements yielded a rate constant 2k of (9.0 0.3) X lo8 M-l sec-I for the reaction of C02COZ- which agrees fairly well with the value of 1.0 X lo9M-’ sec-1 found by Keene, et aL5 Formic Acid Solutions. The carboxyl radical is expected to be formed with G = 5.5 in solutions saturated with NzO and containing low4M formic acid assuming the H atoms do not react with HCOOH or HC02- at this low concentration
+
ea,-
*
+ N,O HzO_ N~ + OH + OH-
(7)
PULSE RADIOLYTIC INVESTIGATION OF THE
OH
+ HCOOH
H20
3207
CARBOXYL RADICAL
+ COOH
(8)
The pK value of formic acid is 3.75, close to that of COOH found above. One should therefore expect that no significant changes in conductivity would occur when formic acid is oxidized. The changes should only be determined by the difference in mobility of HCOO- and COz-. Figure 4 shows the time de,pendencies of the conductivity and of the 2600 A absorption a t pH 8.1 and of the conductivity alone a t lower pH values (the curve for the optical absorption did not change with pH). Let us at first consider the change in conductivity 20 rsec after the pulse, ie., after possible neutralization processes are over and all equilibria attained. At pH 8.1, there is a slight increase, a t pH 4.7 practically no change, and a t pH 3.6 a very slight increase in conductivity. Knowing the absorbed dose and the G value of 5.5 of COOH, the change in molar conductivity of the solution could he calculated. Figure 5 shows the result. It can be seen that the conductivity changes shortly after the pulse are smaller than 20 ohm-' cmz mol-' showing that protons are neither formed nor used up in a significant amount at any pH. This observation corroborates the pK value of COOH mentioned above which is practically the same as that of formic acid. The conductivity change is not exactly equal to zero, a t all pH values, probably as a result of three effects. (a) The molar conductivities of HCOO- and Cor- are different. AHCOO- is only 47 ohm-' cm2 mol-' as compared to ACO1- = 60 ohm-I cm2 mol-' found above. (b) The pK values of formic acid and carboxyl may not exactly be equal but differ by a few tenths of a unit. (c) Formic acid exerts a buffer effect.
PH
-"I
I
-40 3
L
5
6
7
8
PH
Figure 3. Change in molar conductivity 20 psee and 1 msec after the pulse at various pH values (10-4 M formic acid solutions, saturated with N,O).
The changes in conductivity at longer times after the pulse may now be discussed. Figure 4 shows that a stable value of the conductivity is reached a t pH 8.1 which is higher than the conductivity of the solution before the pulse. From the final value of the signal one calculates a change in molar conductivity of 20 ohm-' cm2 mol-'. This change is about equal to the difference between one-half the molar conductivity of oxalic acid (63 ohm-' cm2 mol-') and the molar conductivity of formic acid (47 ohm-' cm2 mol-'). It seems therefore that at pH S.l the oxidation of two anions of formic acid leads to one anion of oxalic acid 2C02-
c2012-
(9)
which is in agreement with Hart's observation of oxalic acid being the main oxidation product in alkaline solutions.' Since the Conductivity shortly after the pulse a t pH 8.1 also increased by 20 ohm-' cm2 mol-', it must he concluded again that C0,- has a higher molar conductivity than HC0,-. One calculates AC0,- = 47 ZO = 67 (since one anion of HC0,- is consumed per C02- formed) which agrees with the molar conductivity of 60 ohm-' cm2 mol-' found in the experiments with CO saturated aqueous solutions (Figure 3). At lower pH values (4.7 and 3.6 in Figure 4) the final conductivity of the solution is lower than before the pulse. The dependence of the final change in conductivity, ie., after 1 msec, on the pH is also shown by Figure 5. The reaction
+
COS-
+ COOH -%C02 + HCOOH
(10)
leads to a final decrease in conductivity. It is expected that this reaction will become more important as compared to the reaction of eq 9 with decreasing pH. This explains why the final conductivity is lower than before irradiation a t lower pH values. However, at pH values where formic acid is mainly undissociated, the reaction sequence will be HCOOH
+ OH
--f
2COOH -+ GO,
H20
+ COOH
+ HCOOH
(11) (12)
and no change in conductivity occurs since reactants The Journal of Physical Chenislry. Vel. 74, No. 17, 1970
A. FOJTIK, G . CZAPSKI, AND A. HENGLEIN
3208
2600 A
-
-
0 2
1 ms
Figure 6. Upper part: increase in 2950-A absorption of a 10-8 M formic acid solution containing nitrobenzene (5 X 10-6 M ) at pH 6. (A small pulse was used that produced COOH initially with 5 X 10-7 M ) ; lower part: 2600-A absorption of a 10-4 M formic acid solution saturated with a 4: 1 mixture of NzO and 01,pH 6.9.
and products are neutral. This explains the slight increase in the curve for the final conductivity change at the lowest pH values in Figure 5. As already mentioned, the decay curve of the optical absorption of COOH did not change with pH. Measurements of the second-order rate constant for the disappearance of the carboxyl radical were carried out with lo-' M formic acid solutions a t pH values between 2.8 and 7. A rate constant of (9.0 0.3) X 108 M-I set+ was obtained which agrees with that found by Keene, et aZ.5 These authors also found no change in the rate constant with pH. It is concluded that the reactions of COOH with COOH or Cot- are as fast as that of COz- with COz-. Organic nitro compounds such as tetranitromethanela.14and nitrobenzene15 are often easily reduced by electron transfer from organic radicals. If the radical exists in an acid and basic form, a difference in the rate of the electron transfer is often found. The transfer reaction can easily be observed by pulse radiolysis since the half-reduced nitro compounds have very strong optical absorptions. Figur: 6 shows the pseudo-firstorder increase of the 2950-A absorption of a solution M formic acid, 5 X 10-5 M nitrobenzene, containing and 2.4 X 10Wz M NzO. I n such a solution, the hydrated electron is scavenged by N20. The OH radical reacts with formic acid to form the carboxyl radical during the pulse. Subsequently, the carboxyl radical transfers an electron to nitrobenzene to yield the anion CeH5NOz- which has strong absorption in the ultraviolet (egia 11ooO M-' cm-') and is relatively long, lived (several milliseconds a t pH 7).'5 Experiments of this kind were carried out at different pH values. Figure 7 shows the half-time of the increase in the 2950 A absorption of CsH5NOz- at various pH values. It can be seen that the half-life changes over about 2 pH units by a factor of about 2. Apparently, COOH reduces nitrobenzene a little slower than CO,-. A pK
*
The J o t ~ m of l PhyaiCal Chemislry, Vol. 74, No. 17.1870
3
L
5
6
7
Figure 7. pH dependence of the half-time of firseorder increase at 2950 A of a pulsed solution containing 5 x 10-6 M nitrobenzene.
*
value of COOH of 3.9 0.2 is determined from the turning point of the curve which agrees with the pK value obtained above. COOH transfers an electron to nitrobenzene with k = (5.6 1) X lo8M-' sec-l and COz- with k = (1.0 0.2) X 109. Experiments were also performed with tetranitromethane as electron acceptor. I n this case, the rate constant was found to be equal to (4 1) X lo9and independent of pH. If COOH already transfers an electron in a diffusioncontrolled reaction, an enhancement of the rate for COz- cannot be expected. Experiments were also performed to show that electron transfer can occur from COz- to 02.A lo-' M formic acid solution was pulse-irradiated under an atmosphere of an NzO: O2= 4: 1 gas mixture at pH 8. Under these conditions, the electrons are almost totally scavenged by NzO. The OH radicals attack formate anions while most of the H atoms react with Oz. The Con- ions formed can subsequently transfer its electron to 02.If all these reactions take place at should be present in the diffusion-controlled rates, 02solution with G = 6 afte; the pulse. The lower part of Figure 6 shows the 2 W A absorption of this solution as a function of time. It can be recognized from a comparison with the first picture in Figure 4 (oxygen free solution) that the 2600-A absorption disappears much slower. I n fact, Oz- very slowly disappears in alkaline solutions since the reactions HOz 0%and 0 2 02-have small rate constants.16 It is therefore concluded that the reaction
*
*
*
+
coz- +
0 2 40 2 -
+
+ coz
is fast and occurs during or shortly after the pulse in Figure 2. (13) A. Henglein and J. Jasper&2.Phys. Chem. (Fsonkfurt om Main), 12, 324 (1957). (14) K.-D. Asmus, A. Henplein. M. Ebert. and J. P. Keene, Ber. Bunacnoes. Phya. Chcm., 68,657 (1964). (15) K;D. Asmus. A. Wiamr. . . and A. Hendein, {bid.. 70, 862 (1966). (16) J. Rabani and 8. 0 . Nielsen. J . Phys. C h a . , 73, 3736 (1970).
