Kinetics and mechanisms of the reaction between carbon monoxide and copper(I1) in aqueous solution

J . J . BYERLEY
Department of Chernical Engineering, University of Waterloo, Waterloo, Ontario
AND

E. PETERS
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Department of Iifetallurgy, University of Briti~lzColumbia, Varzcouver 8, British Colun~bia Received June 24, 1968 The kinetics of the reduction of copper(I1) to copper(1) by carbon monoxide in aqueous solutions have been investigated at 120 'C and carbon monoxide pressures up t o 1360 atm. The reaction is hon~ogeneous and proceeds by two paths, one of which is virtually independent of carbon monoxide pressure due to the formation of a stable cuprous carbonyl complex Cu(CO)+. The second reaction path contains both a pH-dependent and pH-independent component. The rate-determining step in both paths appears to be the decoluposition of a carbon lllonoxide insertion complex by a cupric ion. Complexing ligands such as acetate were observed t o have a minor inhibiting effect on the overall reaction.
Canadian Journal of Chemistry, 47, 313 (1969)

Introduction Carbon monoxide reduces a number of metal ions under pressurized conditions and elevated temperatures. The kinetics and mechanisms of many of these reactions, for example, silver(1) (1-3), nickel(I1) (4), cobalt(I1) ( 5 ) , and mercury(1I) (6), are described in the literature. The reaction of copper(I1) with carbon monoxide was first studied by Bauch, Pawlek, and Plieth (1) who reported a first-order dependence on carbon monoxide and a second-order dependence on dissolved copper. McAndrew and Peters (7) using a pressure drop technique (8-10) reported that the overall reaction takes place in 2 stages; the first stage which may be represented by the stoichiometry

P I

- d[Cu(ll)]
dt
=

k,

[Cu(II)] [Cu(I)] [H

+I

The reaction mechanism postulated from the kinetic evidence centered on the formation of carbon monoxide insertion complexes such as

It is now possible, through a combination of the earlier information and new data, especially that obtained at high carbon monoxide pressures, to provide a much more comprehensive understanding of the reaction.

is followed by a second stage described as a further reduction to metallic copper, hydrolysis or disproportionation depending on prevailing chemical conditions. In a previous paper the present authors (11) indicated that at low initial copper levels the process would proceed only through the first stage providing the carbon monoxide pressure was maintained at a sufficiently high value to stabiiize the cuprous ion. Under these conditions it was found that the kinetics of the homogeneous reactions described by reaction [ I ] were expressible by a 2 term rate law

Experimental
A 1 chen~icalswere reagent grade and used without 1 further purification. Carbon monoxide (99.5 % minimum) was supplied by the Matheson Company. The copper(I1) solutions employed in the kinetic study were prepared by diluting standardized stock solutions. Most experiments were carried out in acetate buffered soluttons. The progress of the reaction of copper(I1) with carbon monoxide was followed spectrophototnetrically using a titanium alloy cell which fitted directly into the sample compartment of a DK-2 ratio-recording spectrophotometer. This cell has been described in detail in the literature (12). The spectrophotometer was modified somewhat to permit the recorder pen carriage to be driven at constant speed while the wavelength scroll remained fixed at a desired wavelength (approximately

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750 mb for cupric acetate; the absorption peaks are temperature dependent). This arrangement produced a continuous record of optical density change as the copper(I1) species was reduced. The experimental procedure consisted of filling the reaction cell (total liquid volullle 1 cc) with copper(I1) solution using a hypodermic syringe. The remaining volume in the cell was flushed with nitrogen and carbon n~onoxidethrough the exhaust valve on the side of the vessel. With the cell placed in the sample compartment of the spectrophotometer, the temperature was raised to 120 "C under a pressure of about 20 at111 of carbon monoxide. A thermistor temperature controller provided temperature regulation to within i0.3 "C. When the reaction temperature was reached, the desired carbon monoxide pressure was applied, and the solution was immediately agitated for 2 min by a magnetic plunger. The reaction thus being initiated was allowed to proceed without furlher agitation' since the solubility of carbon monoxide at the applied pressures (68 to 1360 atm) was at least 5 times that required for complete reduction of the dissolved cupric salt.

Experimental Results The General Form of the Rate Law Three typical experimental curves with optical density replaced by copper(1I) concentration showing the reduction of cupric acetate by carbon monoxide are given in Fig. 1. This characteristic "'S" shape was observed for all experiments in the acetate buffered system except when certain extreme chemical conditions were applied. Under these conditions (discussed later) it was possible to virtually eliminate the initial downward curvature. Curves of the type shown in Fig. 1

were consistently found to yield maximum slopes at the point where 50% of the copper(11) had been reduced regardless of the initial copper(I1) concentration. The rate at this mid-point was found to be the most reproducible stage of the experiment (normally within 5 %) and thus was selected as the reaction parameter for most experiments. Examination of the experimental curves shown in Fig. 1 indicates a definite dependence of reaction rate on copper(I1) and acid concentrations. Although a consideration of these variables (along with the carbon monoxide dependence) has resulted in a preliminary rate law formulation, given in the paper cited earlier, it is appropriate to repeat briefly this discussion to facilitate a clear understanding of the final rate law. Figure 2 shows the results of graphically differentiating curves of the type shown in Fig. I. These curves which are nearly symmetrical about the 50% reduction point, indicate a rate law of the form

In this expression the product of the concentrations of 2 copper species is the dominant term

A-

0,0096M 00096M 0,0048M

0 25M

0.50M 0'50M 0.50M

; 8

E
X " D
F

BC-

0,50M 0 25M

rT
W

a a
0
0

20

40

60

80

100

120

140

TIME (mini

FIG.1. Typical experimental curves for the reduction of copper(I1) by carbon monoxide: PC, = 68 atm; temperature = 119.4 "C.
'Agitation during the course of the reaction did not produce any detectable change in the rate of the reaction.

FIG.2. Differential plot showing - d[Cu(II)]/dt vs. [Cu(II)] for 3 initial copper(I1) concentrations: 0.25 M NaOAc; 0.50 A4 HOAc; Pco = 68 atm; temperature = 119.4 "C.

BYERLEY AND PETERS: CO AND Cu(I1) IN AQUEOUS SOLUTION

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whereas the second term is added to account for the initiation of the reaction which must be dependent on copper(1I) alone. Further evidence to support the form of eq. [3] is found through maximum rate measurements. The maximum rate still retains some contribution from the rate due to the second term but this may be neglected. Figure 3 shows a plot of maximum rate for a series of experiments using different initial copper concentrations. A linear dependence on [Cu(II)][Cu(I)] is apparent. The zero intercept arises because at the point of measurement the concentratioll of copper(I1) is about equal to the concentration of copper(1).
COPPER(U)
G9

+ k,'

[CU(II)]~
-

W+I

where k,' = A'K,, k,' = B'K,, and Ki is thc ionization of acetic acid.

COPPER
4
I

( 1 ) X 70'

(mo'e/l)2

1
I

2
I

5
I

6
I

7
1

8
I

FIG. 4. Dependence of maximum rate on l/[HOAc]: 0.0096 M initial Cu(11); Pco = 68 atm; temperature = 119.4 "C.

FIG.3. Dependence of niaxilllum rate on [Cu(II)] and [Cu(II)] [Cu(l)] at 50 % reduction: 0.25 IM NaOAc; 0.50 M HOAc; PC, = 68 atm; temperature = 119.4 "C.

The dependence of maximum rate on the reciprocal of acetic acid concentration is shown in Fig. 4. In view of this result, eq. [3] may be rewritten in the following form

S B

, [CU(II)~[OAC-]l
- - -

[H OAc]

Under the conditions prevailing in this series of experiments only the form of the dominant first term appears justified although it does not seem unreasonable to expect the same acid behavior to be reflected in the second term. Further discussion of this point will be given later. By using the expression for the ionization constant of acetic acid, eq. [4] may be rewritten in terms of a new set of rate constants

~ The c o m ~ o s i t i o ofl the solution used in these experiments is such that free cupric ions ~ i o u l d form a negligible part of the total copper(I1) concentration while the coilcentrations of Cu(OAc)' and Gu(OAc), are present in significant concentrations. Figure 4 may be used to illustrate the inhibiting effect of increasing acetate complexing on the reaction rate by simply selecting a point 011 each curve of equivaleilt [NaOAc]/ [HOAc] ratio. This result indicates that the diacetate complex which increases in concentration on addition of sodium acetate apparently has a somewhat lower reactivity than the monocetate. A portion of the decrease in rate at constant [NaOAc]/[HOAc] is probably due to a salt effect which would cause an increase in the ionization constant of acetic acid and thus an increase in hydrogen ion concentration. No attempt was made to resolve the complexing effect from the rate constants although experiments carried out in perchlorate media, which is considered a very weak complexing ligand, correlated quite well with rates obtained by extrapolating acetate data to "zero9' complexing.

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CANADIAK JOURNAL OF CHEMISTRY. VOL. 47, 1969

1 4

0
0

The form of eq. [8] suggests a method of resolving the rates due to the first and second terms. The intercept of Fig. 5 is an estimate of the rate due to the first term. The additional rate at a particular carbon monoxide pressure is the contribution from the second term. Thus a closer inspection of tile 2 individual terms in the rate expression and a resolution of their rate constants is possible under high pressure conditions.
C O P P E R (111
C
-

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@C

360

240

323

4C3

480

5EO

40

720

C A R B O N ';lOhOXIDE

PRESSURE !at,-)

FIG. 5. Effect of carbon monoxide pressure on maximum rate: 0.0096 ;Vf initial Cu(II), 0.25 M NaOAc; 0.50 IMHOAc; temperature = 119.4 "C.

0 0113M

Effect of Carbon Monoxide Press~~re The effect of carbon monoxide pressure on the reaction rate is recorded in Fig. 5. This plot indicates that the rate of reactioil increases very little over the pressure range of about 60 to 680 atm. 1 1view of the fact that the maximum rate is 1 rather insensitive to large carbon monoxide pressure variation, it is reasonable to assume that the pressure-dependence is primarily related to the second term of the rate law. This can be interpreted in terms of a stable cuprous carbonyl (10) complex given by the equilibrium

5c 4 .

FIG 6.

Resolution of pressure-dependent and pres-

sure-independent teriils uslng [Cu(II)] as the variable: 0.25 A4 NaOAc;O.SO 12.I HOAc; temperature = 119.4 C.

The concentration of Cu(CO)+ can be written as

[7]

[Cll(CO)+]

K [CLI',] [CO] 1 K[CO]

where [Cu+,] is the total moilovalent copper. Since K is known to be large, eq. [7] loses the pressure-dependei~ce axid [Cu(CO) ] [Gu ,I. Thus, with the equilibrium of eq. [6] shifted far to the right, the pressure effect would pertain only to the term not iilvolving Cu(l). The effect of pressure on the first term would only become significant when the CO pressure is so low as to shift the Cui-CO equilibrium to the left. The form of Fig. 5 implies that when the CO pressure is above 60 atm a linear dependence on CO pressure can be assigned to the secoild term of the rate expression. Equation [ 5 ] can be written as

5 2 COPPER(IO x COPPER(r) x 10 (rno~e/i)

FIG. 7. Dependence of total rate, first term rate and second term rate on [Cu(Il)][Cu(I)] or [Cu(I1)lZ, total rate and second term rate measured at 400 atm (Fig. 6): 0.25 M NaOAc; 0.50 IMHOAc; temperature = 119.4 OC.

BYERLEY AND PETERS: CO AND Cu(I1) IN AQUEOUS SOLUTION

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Recorded in Fig. 6 is a series of experiments similar to those shown in Fig. 5 except that 3 different initial copper concentrations were investigated. Figure 7 presents the graphical data taken from Fig. 6. Curves A and B are plots of the total rate at 400 atm and the first term rate vs. [Cu(II)][Cu(I)] and give the expected linear relationships and zero intercepts. Curve Cis a plot of the rate due to the second term and is also linear in [Cu(II)][Cu(I)] which is equivalent to [Cu(11)I2 at 50 % reduction. Equation 8 may thus be rewritten in the form

TOTAL R A T E
1st T E R M R A T E

o
6

2 n d TERM R A T E

; ;

where k,' = 5.43 x s-' (f10%) and k," = 5.70 x s-' atm-I ( 1 2 0 7 3 , concentration of NaOAc = 0.25 M, temperature = 119.4 "C. Another series of experiments was carried out in which the []t-It 1 was varied instead of the

05

1-0

15
A C I D (mole/

2.0

I/ACETIC

11 -I

FIG. 9. Dependence of total rate, first term rate, and second tern1 rate on l/[HOAc], total rate and second term rate measured at 400 atm (Fig. 8): 0.0096 M initial Cu(II), 0.50 M NaOAc; temperature = 119.4 "C.

=c '
x

--.-/----

50

10 6

240

320
PQESSURE

40i
(?

480

C A ~ B O Nl , i O U l i l D E

:T:

FIG. 8. Resollition of pH-dcpcndent and pH-independent terms: 0,0096 Mini&, Cu(II); temperature = 119.4 'G.

[Cu(IL)]. These results are shown in Fig. 8. Curve A of Fig. 9 is a plot of the total rate of the reaction at a CO pressure of 400 atm. The curve does not pass through the origin which suggests a pHindependent component of the reaction. This result was not evident in the data obtained from the acid series at 68 atm of carbon monoxide. Thus the pH-independent component must be contained only in the second term of the rate law. Curve B sho~vs expected inverse linearity of the the first term along with a zero intercept. In view of these the may be described by a 3 term rate expression

where the rate constants as obtained from the data in Fig. 9 are given as follows: lc, = 4.24 x s-I (11073, k, = 1.40 x s-' atm-I (+20 %), k , = 1.15 x s-I M - I atm-' Qf- 15 %), concentration of NaOAc = 0.50 M , temperature = 119.4 "C.

Through the use of the pressure variable it is possible to enhance the contribution of the pressure-dependent terms which at modest pressure account for less than 10 % of the maximum reaction rate. Estimation of the second term rate constant k," has, up to now, been made on the

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basis of maximum rates which can produce large errors. Initial rate measurements at low pressure were also found to suffer from large errors not only because of the inherent difficulty associated with initial rate measurement but also because the reaction is changing very rapidly from a pure cupric dependence to a cupric-cuprous dependence. A series of experiments were performed at carbon monoxide pressures from 68 to 1360 atm. The experimental curves are reproduced in Flg. 10. The gradual elimination of the characteristic "'SI'shape can be explained in terms of a superposition of curves, a convex curve due to the second-order dependetlce of copper(I1) in the second term and an "'Skurve with a very slow initial downward curvature lncreaslng only when the copper(1) le\el becomes significant. As the second term contribution becomes large with increasing carbon monoxlde pressure the initial downward curvature disappears. Using a one term approximation of eq. [9], that is

FIG. 11. Arvhenius plot for the reduction of Cu(I1) by carbon monoxide: 0.0096 M initial Cu(II), 0.25 ,' T i NaOAc; 0.25 M HOAc; PC, = 68 attn.

the average value of k2" was found to be 5.02 x s-I atm-l. This average does not include the evaluatioi~ k," taken from the experiment of at 68 atm. It should be noted that the value of the ionization constant of acetic acid is affected by

hydrostatic pressure. This pressure dependence which has been reported by Hamann and Strauss (13) shows that the ionization constant varies from 1.95 x to 5.4 x 10-' at 25 "C in the pressure range 1 to 3000 atm. This factor has been taken into account when calculatinglc,".

Tlze Ter~iperatureDependence The effect of temperature on the reduction of copper(I1) was investigated over the temperature range 100 to 123 "C.The rate constants plotted in Fig. 11 are those which pertain to the dominant term since they were obtained from maximum rate measurements. No attempt was made to separate the temperature dependence of the smaller terms. From the slope of t h ~ s Arrhenius plot, an experimental activation of 25.8 F 1.0 kcall mole was calculated.
Reaction ~Vechanism A reaction mechanism may be postulated which is compatible with the kinetic evidence summarized in the 3 term rate law given by eq. [lo]. This mechanism which defines 2 reaction paths may be represented as follows
OH

T I M E (mn:

FIG. 10. Alteration of experimental curves by increasing carbon monoxide pressure: 0.0096 M initla1 Cu(lI), 0.125 1 NaOAc; 0.50 M HOAc; temperature = M 119.4 ' C .

PATH A Cu(II)

I + co + 1 ~ T----)(cu-cL-oH)~+ ~0
K a

rapid equilibrium

BYERLEY AND PETERS: CO AND Cu(I1) IN AQUEOUS SOLUTION

Cu(I1) S CO

+ HzO ;----" 1 1 (CU-C-OH)+ + H+

K b

rapid equilibrium

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PATH B
Cu+ f GO fast

Cu(C0)
0

Cu(CO)+

+ Hz0

Kc

(CU-C-OH)

II

+ Ht

rapid equilibrium

112hl

CuH'

+ Cu(II)

fast

2Cu(I) c R t

The rate law derived from this reaction sequence corresponds to

Equation [13] is identical to eq. [lo] if kcKc = k,, kbKb = k,, k,K, = k,, [Cu(CO)+ ] = [Cu(I)], and the stoichiometry is taken into account. The first term does not appear to have a pH-independent component. According to the proposed mechanism the observed pH-independent reaction results from the doubly charged intermediate

where the carbon co-ordinates 2 hydroxyl groups. An analogous equilibrium to reaction r12al could exist

resulting in a singly charged intermediate. The absence of the pH-i~dependent contribution suggests that either this structure is extremely labile and does not exist long enough to react with copper(IH), or the attack of the intermediate

by copper(I1) is too slow to contribute an observable effect. There are 2 important features evident in the proposed mechanism, the insert1011of a carbon monoxide molecule between a metal ion and co-ordinated water molecule, and the decornposition of the insertion complex by another metal ion. The postulation of a carbon monoxide insertion intermediate is not new. The reduction of silver(1) (2, 3, 9) in both acid~cand basic solutions incorporate carbon monoxide insertion complexes into the mechanisms which subsequently undergo decomposition by a metal ion. In the reduction of mercury(1l) (6, 14) and nickel(l1) (4) by carbon monoxide and the metal ion-catalyzed reduction of Mn0,- (6, 14), similar intermediates have been postulated. There is no kinetic evidence for the attack of these intermediates by metal ions to facilitate their decomposition as in the case of silver(1) and copper(I1) reductions. In the development of the reaction mechanism

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not only have insertion complexes been suggested, but also the carbonyl complex (10) Cu(CO)+. In order to account for the pressure-independent character of the first term of the rate law, a fast reaction involving the complexing of Cuf with carbon monoxide has been proposed. This is In contrast to the pressure-dependency of the second term, where carbon monoxide participates in a pre-equilibrium. The Cu' ion does possess the characteristics necessary for carbonyl formation and indeed shows a great affinity for carbon monoxide. The existence of a stable carbonyl clearly distinguishes the Cu(I1)-CO reduction mechanism from the earlier mechanisms proposed for silver(I), mercury(II), and the catalyzed reductio~lof MnO,-. The explanation of the pH-independent term of the rate law appears in the mechanisms in the form of an intermediate exhibiting a protonated carboxyl group. Although the attachment of 2 OM- groups to the same carbon atom lacks stability, the presence of a species sucll as Cu2+ could have sufficient electrophilic character to promote stabilization. Further stability of this intermediate may also be gained by admitting resonance structures such as

allowed by the rate law whereas the overall stoichiometry would require two Cu2' ions. The alternate products to CuH" are copper atoms and a proton. The available thermodynamic data indicates that the formation of such species is energetically inconsistent (8 1.5 kcal/mole) with the activation energy of 26 kca1,'mole observed for the reduction of copper(1I) by molecular hydrogen in which CuH' is the proposed intermediate (16, 17). The final decomposition of GuHf by reaction with another copper(I1) species is regarded as fast and does not affect the kinetics. In strong acid solutions it would be expected to compete with another reaction between CuH' and hydrogen ions which would yield n~olecular hydrogen, i.e.

This reaction was never observed in acetate solutions and would be difficult to obtain because of the slow nature of the overall reaction in strongiy acid solutions due to the reciprocal dependence of the rate on hydrogen ion concentration. The principle difference in the rate-determining step of path A is that the intermediate species

The slow step in both reaction paths is the by attack of the insertion con~plexes copper(I1). In path B the slow step implies the transfer of an H atom or hydride ion H-. It seems reasonable to assume that the copper ion forming the CuHf intermediate comes from the insertion con~plex whereas the attacking copper(T1) acts as the electron acceptor2. Removal of a hydride ion from H, to form CuH' has already been postulated for the mechanism of hydrogen reduction of copper(I1) and thus is not without support (15). The postulation of CuHt permits the use of one Cu2+ ion in the rate-determining step as
'At first glance the species

(or the protonated form) ha< a net positive charge. The charged intermcdiate n ould be a stronger acid than the neutral species

thus allowing the hydrogen to come off as a proton more readily when it is attacked by copper(1l). The result is a simple oxidationreduction reaction. In contrast to the reduction of silver(1) by carbon monoxide in acetate solution the present reaction exhibited only minor sensitivity to the acetate ligand. No attempt was made to resolve this variable nor is it considered in the reaction mechanism.
Acknowledgment The authors gratefully acknowledge the financial support from the National Research Council of Canada.

appears to be a n acid and upon dissociation a proton would be produced. However, the intenl~ediate is sufficiently electron rich so that in the presence of a suitable recipient 1 or even 2 electrons may accompany the proton in which case the result is either hydrogen atom or hydride ion transfer.

BYERLEY AND PETERS:

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AP\D CU(II) IN AQUEOLS SOLUTION

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1. G. BAUCH,F. VON PAWLFK, arsd K. PLIETH. Z. Erzberghau kIetallh~~ttene\~,1 (1958). 11, 2. R . T. MCANDREW E. PETERS.Can. Met. Quart. and 3 , 153 (1964). 3. S. NAKAMURA J. HALPERN.J. AISI.Chem. Soc. and 83, 4102 (1961). 4. E. HIRSCH E. P ~ T E R SCan. Met. Ouart. 3. 137 and . (1964). 5. H. K . F~ALVERSON. D . Thesis, University of Ph. British Colun~bia, Vancouvcr, British Colun~bia. 1966. and 6. A. C. HARKNESS J. HALPERN.J. Ani. Chem. Soc. 83, 1258 (1961). 7. R . T. MCANDREW and E. PETERS. Unuublished observations. 8. R. T. M C A ~ D R E W . Ph.D. Thesis, University of British Columbia, Vancouvcr, British Colun~bia. 1962.

9. R. T. MCAUDRLW and E. PETERS.Can. Met. Quart. 3, 153 (1964). 10. J. J. BYERLEY J. Y . H. LEE. Can. J. Chem. 45, and 3025 (1967). 11. J. J. BYERLEY E. PETERS.S V ~ I D . and Unit Processes Hydromet. Met. Soc. Conf. ~ o l 24. Gordon and . Breach. New York. 1964. 12. J. J. BYERLEY and E. PETERS.Rev. Sci. Instr. 34,819 (1963). 13. S. D . HAMANN LV. STRAUSS.Trans. Faraday and Soc. 51, 1684 (1955). 14. A. C. HARKNESS. Ph.D. Thesis, University of British Columbia. Vancou~er. British Col~~mbia. 1963. 15. J. HALPERU.O ~ ~ a rRev. London. 10. 463 (1956). t. 16. R. G. DAKERS J. HALPERN. &d Gin. J. Ch&.-32, 969 (1954). 17. J. HALPERN, R. MACCREGOR, E. PETERS.J. E. and Phys. Chem. 60, 1455 (1956).

This article has been cited by: 1. Daniele Delledonne, Franco Rivetti, Ugo Romano. 2001. Developments in the production and application of dimethylcarbonate. Applied Catalysis A: General 221:1-2, 241-251. [CrossRef] 2. 1992. Ernest Peters: A biography. Hydrometallurgy 29:1-3, ix-xiv. [CrossRef] 3. Yu. L. Sheludyakov, V. A. Golodov. 1982. Kinetics and mechanism of piperidine carbonylation in the presence of Cu(I) and Cu(II) complexes. Reaction Kinetics and Catalysis Letters 20:1-2, 39-42. [CrossRef] 4. Jack Halpern. 1981. Oxidation of Carbon Monoxide by Metal Ions and Homogeneous Catalysis of the Water Gas Shift Reaction and Related Processes. Comments on Inorganic Chemistry 1:1, 3-15. [CrossRef] 5. Albert R. Garber, Paul D. Ellis, Kurt Seidman, Kathryn Schade. 1979. Semiempirical theory of magnetic resonance parameters. I. Theory of chemical shielding constants, using gauge-invariant atomic orbitals, parameterization, and carbon-13 chemical shifts. Journal of Magnetic Resonance (1969) 34:1, 1. [CrossRef] Can. J. Chem. Downloaded from www.nrcresearchpress.com by 182.0.85.188 on 05/10/12 For personal use only.