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Acknowledgment. G.R.C. Is Grateful To IC1 Ltd. For A A: A
Acknowledgment. G.R.C. Is Grateful To IC1 Ltd. For A A: A
Acknowledgment. G.R.C. Is Grateful To IC1 Ltd. For A A: A
The aquation rate constants for the acidopentaammine- the other hand favor an associative interchange, la, for the
chromium(II1) complexes, Cr(NH3)5X2+, X- = NCS-,' water exchange reaction on the basis that a negative volume
CC13C02-,2 C F ~ C O Z -Cl-,4
, ~ Br-, and I-,5 have been deter- of activation (-5.8 cm3 mol-') has been obtained. It is not
mined previously. Different ionic strengths and media were clear therefore from these various studies whether the in-
used, however, and a meaningful comparison of data is terchange mechanism involved is associative or dissociative.
therefore difficult. Duffy and Earley4 have determined the The aim of this investigation is to extend previous studies
rate constants for water exchange of Cr(NH3)5H203+ as well to include all relevant kinetic and thermodynamic measure-
as the anation of this complex with C1- and NCS- and have ments, thus enabling a firm mechanistic assignment to be
proposed a dissociative interchange (Id) mechanism. For a made.
part of their study (the NCS- anation reaction), NaBr was Experimental Section
used to adjust the ionic strength and the inner- and outer-
sphere associations of Br- appear to have been neglected. It Materials. Literature methods were used to prepare the complexes
[Cr(NH3)sH201(C104)3,9 [C~(NH~)S(NCS)I(C~O~)~,~~ [Cr(N-
has been observed in earlier work that after allowing for H ~ ) S ( O ~ C C C ~ ~ ) I ( C ~[Cr(NH3)5(02CCF3)I(C104)2,"
O~)I~H~~,~~
outer-sphere association (Kos obtained from kinetics) the rate [Cr(NH3)5CI](C104)2, and [Cr(NH3)5I]Cl2.l3 The complex
constants for C2042-, H C Z O ~ -and
, ~ +NH3CH2C02- are [Cr(NH3)5Br]Br2 was prepared by heating [Cr(NH&H20] (c104)3
about the same as for water exchange. Hence a dissociative (1.0 g) in 50 ml of solution containing 2.5 M NaBr and 0.1 M HC104
I d mechanism has been suggested. Swaddle and Stranks,* on at 50 OC. Crystals of [Cr(NH3)5Br]Br2 were obtained within about
2886 Inorganic Chemistry, Vol. 15, No. 11, 1976 T. Ramasami and A. Geoffrey Sykes
45 min. After filtering the filtrate was again heated at 50 OC when
more product was obtained. This procedure was repeated three to
four times. The bromide salt was converted to perchlorate by grinding
in a precooled pestle and mortar with 70% HC104 till no more fumes
of HBr were evolved. The complex was filtered and recrystallized A
from 1 M HC104 by the addition of ice-cold 70% HC104. Anal. Calcd
for [Cr(NH3)5Br](C104)2: Cr, 12.5; N , 16.82; total halide, 25.6.
Found: Cr, 12.4; N , 16.55; total halide, 25.6. Elemental microanalyses
for other complexes were consistent with the above formulas. Details
of uv-visible spectra, Table I, are in satisfactory agreement with
published values (wavelengths & 1 nm; absorption coefficients within
3-6%).
Perchloric acid (72%, Hopkin and Williams, Analar) was used OkO 400 450 522 550
h!nrn:
without further purification. Lithium perchlorate was prepared from
Li2CO3 and HC104. Solutions of LiC1, LiBr, and LiNCS (all 3 M) Figure 1. Uv-visible absorption spectra of aquopentaammine-
were prepared by metathesis of the potassium salt with LiC104, chromium(II1) (A), trichloroacetatopentaaminechromium(II1)(a),
followed by the filtering off of insoluble KC104 at 3-5 O C . Con- and trichloroacetatoaquotetraamminechromium(II1)(m) in aque-
centrations of C1-, Br-, and NCS- were determined by direct titration, ous solution. [HClO,] = 0.1 M , I = 1.0 M (NaC10,).
and total cation concentrations were estimated by exchanging an
aliquot onto an Amberlite IR-l20(H) ion-exchange column and processes, k,,, can be expressed as in (4). For further details on the
titrating the H+ liberated. The agreement between the two estimations
was within 2% indicating that the amount of KC104 was small. The (4)
determined cation concentration was used in adjusting ionic strengths. methods of determination of kf and k,, see below.
Sodium iodide (BDH, >99.5% purity), trichloroacetic acid (BDFI, Determination of Overall Equilibrium Constants by Spectropho-
Analar), and trifluoroacetic acid (BDH, Reagent Grade) were used tometry. This procedure was used for measuring the equilibrium
without further purification. constants for C1- and Br- complexing with Cr(NH3)5H2O3+ a t 50
Preliminary Experiments. Aquation of Cr(NH3)5CI2+ and Cr- OC,[H+] = 0.1 M, and I = 1.00 M (LiC104). Absorption changes,
(NH3)5Br2+ a t 50 "C, [H+] = 0.10 M and I = 1.00 M (LiC104), AA, were determined at 225 nm for C1- and 265 nm for Br- as a
occurred with retention of isosbestics a t 360, 420, and 493 nm (for function of halide concentration. At these wavelengths both inner-
C1-) and 361, 424, and 495 nm (for Br-). Retention of five isosbestic and outer-sphere complexes absorb. The outer-sphere complexes are
points was also observed for the aquation of Cr(NH3)512+ at 20 "C, known to form,14 since there is an immediate increase in the absorbance
[H+] = 0.1 M and I = 1.00 M (LiC104). Final spectra correspond on mixing Cr(NH3)sH203+ and halides. The absorbance changes
with that of Cr(NH3)5(H20)3+. The spectrophotometric changes L4 observed are therefore related to the overall equilibrium constant,
Kos + K o s K ~ s , 'where
-
in the cases of Cr(NH3)5(NCS)2+, Cr(NH3)5(02CCCl3)*+, and ~ Kos and K I are
~ as defined in (5) and (6).
Cr(NH3)5(02CCF#+ occurred slowly at 50 OC, [H+] = 0.1 M for
KOS
NCS- and 0.01 M for CC13CO2- and CF3CO2-, I = 1.00 M (LiC104). Cr(NH3)5H,03++ X- Cr(NHJ5H2O3+,X- (5)
Spectrophotometric changes in all these cases were more significant
in the uv region than in the visible region. Product analyses were KIS
carried out using ion-exchange separations on Dowex 50W-X2 resin, Cr(NH,),H,O", X- -
4 Cr(NH,),XZt + H,O
in order to assess the reaction paths and interplay of side reactions. The overall equilibrium constant was obtained from the ratio of
The complex, Cr(NH3)5(02CCCl3)*+, alone gave direct evidence for intercept to slope of plots of ( L 4 - l against [Xl-l. The concentration
another minor reaction product along with Cr(NH3)5H203+ after of X- was in large excess over that of the complex, [Cr(NH3)5H2O3+]
18 h a t 50 OC, [H+] = 0.02 M, I = 1.00 M (LiC104). Using the =6X M for C1-and [Cr(NH&H203+] = 8 X M for Br-.
micro-Kjeldahl technique and chromate analysis, the minor product It is assumed that second ion-pair formation and changes in activity
was found to have a nitrogen to chromium ratio of 4.1:l.O. Its elution coefficients by replacing C104- with halides are not effective.
behavior is consistent with a 2+ charge. This product is most probably Determination of Equilibrium Constants by Ion Exchange.
Cr(NH3)4(H20)(02CCC13)*+. Therefore ion-exchange and spec- Equilibrium constants, in this case KosKls, (7), were determined by
trophotometric measurements indicate that the primary reaction is
( l ) , in all cases except X- = CC13CO2-. With Cr(NH3)5(02CCC13)*+,
(7)
Cr(NH3)5H203t+ X -
kaq
Cr(NH3)5X2t+ H,O -+ (1)
the separation of equilibrated products by ion-exchange chroma-
a modified scheme tography and analyzing the distribution of chromium(II1) in each
fraction. Solutions were allowed to equilibrate for at least four to
Cr(NH,),H,03+ five k,, half-lives a t 50 OC. The ranges of anion, hydrogen ion, and
+ CcI,Co,- initial Cr(NH3)5H203+ concentrations investigated were as follows:
[NCS-] = 0.03-0.08 M, [Cr(III)] = (2-3) X M, [H+] = 0.1
Cr(NH,)S(02CCC1,)2++ H,O (2) M; [CC13CO2-] = 0.4-0.6 M, [Cr(III)] = (5-8) X M, [ H + ]
= 0.01 M; [CF3C02-] = 0.4-0.6 M, [Cr(III)J = (2-3) X M,
[H+] = 0.01 M; [Cl-] = 0.1-0.8 M, [Cr(III)] = (5-8) X M,
[H+] = 0.1 M; [Br-] = 0.2-0.86 M, [Cr(III)] = (8-12) X M,
+ NH,+ [H+] = 0.1 M. The ionic strength was adjusted to I = 1.00 M
has to be considered, where k1 is the rate constant for aquation of (LiC104). All equilibrated solutions (with the exception of CF~COZ-)
ammonia. The spectrum of Cr(NH3)4(H20)(02CCC13)*+ is given were first diluted with twice the volume of ice-cold water, and the
alongside those of Cr(NH3)5(02CCC13)*+ and Cr(NH3)5H203+ in products separated using Dowex 50W-X2 (200-400 mesh) ion-ex-
Figure I . change resin columns (1 cm diameter, 8 cm long) thermostated at
The reactions of X- = NCS-, CC13CO2-, CF3C02-, C1-, and Br- 0 "C. The equilibrated solutions were diluted with twice the volume
with Cr(NH3)sH2O3+ gave rise to the acidopentaammine as the only of perchloric acid at pH 2.0; in the case of CF3C02-- ion-exchange
product and identification of products as well as spectrophotometric separations were carried out at room temperature (ca. 20 "C) to avoid
changes observed are consistent with equilibration reactions as in (3). crystallization of Cr(SH3)5(00CCF3)2t. No direct evidence for
secondary products was seen in the case of CC13CO2-, and k,, >>
kf kl under these conditions. With I-, in an attempt to estimate KosKrs,
Cr(NH,),H,03+ + X- -3 Cr(NH,),XZ+ + H,O (3) a modified technique was used. Reaction solutions (25 ml) (which
k w
had [I-] = 0.66 and 0.78 M, [Cr(NH3)5H203+] = (2-4) X M,
The rate constants, kf, could be determined directly, if (3) proceeds and [H+] = 0.1 M) were thermostated for 90 min under air-free
essentially to completion. The rate constants for the equilibration conditions then diluted with an equal volume of ice-cold deaerated
Acidopentaamminechromium(II1) Complexes Inorganic Chemistry, Vol. 15, No. 11, 1976 2887
Table VIII. Summary of Equilibrium Constants for Inner- and Outer-Sphere Associations of X- with Cr(NH3)5H,03+at 50.0 "C,
I = 1.OO M (LiCIO,)
I I
0 0.5 10
[Cl-] (M)
Figure 6. The [CI-] dependence of pseudo-first-order rate con-
stants, keg, for the equilibration of chloride with aquopenta-
amminechromium(II1) (A), and with chloropentaamminechromi-
um(II1) ( 0 ) at various [H+],50 "C, I = 1.0 M (LiCIO,).
0 0.5 10
[NCS-] (M)
I
'u I ; 0
0 0.5 10
[Br-I ( M )
Figure 7. The [Br-] dependence of pseudo-first-order rate con-
stants, k,,, for equilibration of bromide with aquopentaammine-
chromium(II1) (A) and with bromopentaamminechromium(II1) (c)
at various [Ht], 5OoC,Z= 1.0 M (LiCIO,).
[CCI,C021 ( M )
Figure 4. The [CCl,CO,'] dependence of pseudo-first-order rate
constants, kobsd, for the reaction of aquopentaamminechromium-
(111) with trichloroacetate at [Ht], I = 1.0 M (LiClOJ.
01 1 1 I
0 2 4 6
[NCS-]-'(M-')
Figure 8. The dependence of k0bsd-l on [NCS-].' for the NCS-
anation of aquopentaamminechromium(III) at 50 "C, I = 1.00 M
(LiClO,).
kan
Cr(NH3),H203+,X-
O ~ + , Cr(NH,),X*+
kaq
could be considered for all the equilibrations.
+ H,O
(8)
The rate
Acidopentaamminechromium(II1) Complexes Inorganic Chemistry, Vol. 15, No. 11, 1976 2889
Table IX. Summary of Rate Constants for the Formation ( k f ) Table X. Summary of Activation Parameters for the Forward
and (/can) and Aquation (kaq) of Cr(NH3),X('n)+ Complexes at Rate Constants ( k f )for the Reactions of X' with Cr(NH,),H,O3'
50.0 " C , Z = 1.00 M (LiClOJ
Mf*, A&*,
104kf 104k,,,d Ligand X' kcal mol-' cal K-' mol-' Ref
Ligand X- M-1 s-l s-' 104k,,, Ref
NCS- 24.4 3 4
NCS- 4.16 i: 0.08
6.12 f 0.011 f 0.001 This work ccl,coa- 25.2 i: 0.32 2.2 i: 1.0 This work
0.55 c1- 25.6 2 4
3.3 i 0.15= 4 HC204- 26.1 9.4 6
cc1,co,- 1.81 f 0.02 0.51 0.01 *
This workf c,o,=- 24.9 7.8 6
CF3kO2.- 1.37 f 0.04 0.50 f 0.02 This work +NH,CH,CO,' 25.3 f 0.93 5.6 f 2.9 This work
c1- 0.69 f 0.02 1.75 f 0.01 This work H,O" 23.2 0 8
Br-
0.53 i: 0.04b
3.71 f 0.34c 12.5 0.2 *
4
This work
Brb *
21.9 1.2 -4.0 ?r 3.9 This work
I' 102 f 3 This work Activation parameters for water exchange. From a least-
+NH3CH2C02- 7.82 f 0.74e 14.2 i I squares treatment (with unit weighting) of k,,Kos values at each
3.98e temperature.
HC,O,' 6.45 5.86 6
c (j2= 29.1 6.46 6
realistic for slow equilibrations such as those involved in this
H~O, 13.7e 8
study. Even this technique, due to lengthy procedures,
Temp 45 " C , I = 0.11 M (NaC10,). Temp 45 " C , I = 1.71 M nonstoichiometric recovery of total Cr(II1) (f3%), and the
(NaCIO,). Computer fit of the kinetic data at 50.0 "C with an
allowance for ion-pair saturation gives k f = (6.32 f 1.3) X
possibility of resin catalyzed processes, requires careful as-
M-l s-',KOS = (0.78 i: 0.44) M-'. k,, = kg/Kos. e Extrap- sessment. This same technique has been used to obtain even
olated data. Data for this study further refined following T. smaller equilibrium constants, KOSKIS,than those encountered
Ramasami and A. G. Sykes, J. Chem. Soc., Chem. Commun., 318 in the Cr(NH3)5X2+ series, for example, a value of M-'
(1976). for X- = I- in the case of the Cr(H20)5X2+ series.20 Dif-
ficulties experienced in determining small equilibrium constants
constants for the equilibration, k,, are therefore given by (9). have been discussed p r e v i o u ~ l y . ~Equilibrium
~-~~ constants,
kanKos [X-I
KOSKISobtained by ion-exchange and kinetic methods in this
ke, = k,, + (9) study, are, however, in g o d agreement (Table VIII). The rate
1 + Kos P-1 conitants kf and kaq and the equilibrium constant (kf/kaq =
When X- = NCS- and CC13CO2-, the rate of aquation, kaq, K~sKos)could be obtained with sufficient accuracy (see Table
makes negligible contribution to the rate constant, keq. VIII) by kinetic methods, though in the case of Br- uncer-
Therefore (9) reduces to (10). However, only in the case of tainties are involved in kf due to outer-sphere complexing.
Since the ion-exchange procedures used in the separation of
kobsd = kanKOS[X-l/(l + KOS[XI) (10) Cr(NH3)5X2+ involved only 4-5 h, the aquation of Cr-
X- = NCS- is Kos[X-] significant compared to 1, so that a (NH3)5Br2+ at 0 "C (kaq at 0 OC = 4.5 X s-l) is alone
less than first-order dependence is observed, Figure 3. The relevant. The inaccuracies even in this case are minimal. This
intercept and intercept/slope ratio of a plot of (k&d)-' against is supported by the observation that in a blank experiment
[NCSI-' give kan and Kos, respectively, Figure 8. When Kos performed on Cr(NH3)5Br2+, 98% of Cr(II1) could be re-
<< 1, as in other cases of X-, the forward rate constant, kf, covered as Cr(NH3)5Br2+ under the conditions employed in
is given by (1 1). When X- = I-, the rate of aquation, kaq, equilibrium constant estimations. The reproducibility of
equilibrium constants estimated by the ion-exchange method
kf = kanKos [x-I (1 1) confirms the validity of data, and errors are well within the
accuracy of the technique.
predominates over the forward step in (9) and so keq ap-
The results obtained with X- = NCS- give direct kinetic
proximates to kaq. The rate constants, keq, were found to be
evidence for outer-sphere association in Cr(NH3)5H203+
independent of the identity of the starting complex, whether
anation studies. It is assumed that a mechanism involving
this was Cr(NH3)5H203+ or Cr(NH3)5X2+,with X- = C1- outer-sphere association also holds for X- = CC13CO2-,
and Br-. As the kinetics of the anation with CC13CO2- were
CF3C02-, C1-, and Br- and spectrophotometric and kinetic
monitored at the isosbestic point, 505 nm, for the process data are consistent with this. The outer-sphere association
involving the product Cr(NH3)4(H20)(02CCC13)2+the term
constants, Kos, obtained by kinetic procedures for NCS- at
kl in (2) does not contribute. Rate constants k f , kan, and kaq 50 OC, I = 1.00 M (LiC104), Table VIII, compare well with
are listed collectively with those for other comparable ligands
the previously reported Kos values such as 1.1 M-" at 50 OC
in Table IX (see below).
Activation parameters for the forward rate constants, AH; for Cr(NH3)5H203+,HC204- and 1.0 M-' at 25 "C for
Cr(H20)63+,NCS- 25 at I = 1.0 M (NaC104). The outer-
and AS;, for the C1- and NCS- anation of Cr(NH3)5H2O3+
sphere association constants, Kos, reported by Duffy and
have been reported by Duffy and Earley4 (in the absence of Earley4 for Cr(NH3)sH203+ from spectrophotometric
Br-) and have now been obtained for the anation with X- =
Br- and CC13CO2- (see Table X). Activation parameters for measurements are around (3 f 2) M-' for C1- and (10 f 4)
M-l for NCS- at I = 0.16 M (NaC104), 23.3 "C. As King
the aquation reactions, AH,,* and AS,,:, for all six Cr-
(NH3)5X2+ complexes are available in the literature. For X- et a1.26have pointed out, it is not always possible to obtain
= Br- and I-, AHaq*and AS,,* have been redetermined.
Kos by spectrophotometry for weak outer-sphere complexes.
This is especially true when [X-] is large and spectrophoto-
Discussion metric contributions from second ion-pairing and activity
The equilibrium constants for inner- and outer-sphere changes may also contribute. An examination of spectro-
associations are summarized in Table VIII. The need to photometric changes in the uv range for outer-sphere asso-
estimate Kos independently with high accuracy limits the ciation of X- = CCbC02-, C1-, and Br- with Cr(NH3)5H2O3+
+
usefulness of Kos Ko,&Is. Kinetic measurements also have indicated that when [X-] = 0.1-0.9 M, Kos values cannot be
been found to be useful only in cases where equilibrium determined accurately since spectrophotometric changes due
constants are large. The method involving ion-exchange to the second outer-sphere association process may also be
separation of equilibrated solutions appears to be the most contributing. Outer-sphere association constants of about 1.O
2890 Inorganic Chemistry, Vol. 15, No. 11, 1976 T. Ramasami and A. Geoffrey Sykes
M-I are to be expected for 3+,1- ions from theoretical cal-
culations at I = 0.5 M.6,27The value of Kos for X- = NCS-
obtained in the present kinetic studies is consistent with such
-301
theoretical values. Failure to observe any form of ion-pair
saturation in the kinetic studies with X- = CF3C02-, Cl-, and
CC13CO2- requires further comment. With the first two, the : I /
//
.CI-(5)