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1214
Reagents
Distilled water is used in all preparations. The following stock solutions should be prepared in advance and filtered through Celite:
1. 1.00 M HClO4 , from dilution of a standardized
concentrated solution of perchloric acid to 1.00
dm3.
2. A standardized ferric ion solutionca. 0.2 M
iron(III)prepared from Fe(ClO4 )3?xH 2O and
made up to be exactly 0.400 M in HClO4. This
corresponds to about 25 g of Fe(ClO4 )3?xH2 O dissolved in 1.00 M HClO4 (100.0 cm3 ) with dilution to 250.0 cm3. Because the water content of
solid ferric perchlorate is variable, it is not a
simple matter to make up the solution to a particular iron(III) concentration. If analysis shows
it to lie in the range 0.17 to 0.23 M no adjustment is necessary.
3. 2.00 M NaClO 4 , prepared by dissolving
NaClO4?H2O (280.92 g) in water and diluting to
1.00 dm3 .
4. A solution approximately 1.5 10 {4 M in
NaSCN1 and 1.00 M in NaClO 4.
The stock solutions are stable for many weeks. The
iron(III) stock solution is conveniently standardized by
atomic absorption spectroscopy.
In the preparation of the iron(III) reagents used in kinetic determinations the stock solutions are more readily
dispensed using adjustable pipets (0.2001.00 cm3 , 1.00
5.00 cm3 capacity) fitted with disposable tips rather than
conventional all-glass graduated pipets. (C AUTION: Perchloric acid solutions are corrosive and should not be pipetted
by mouth. On completion of the experiment all acid residues should be combined and neutralized by the careful addition of solid sodium carbonate. The resulting solution
should then be disposed of in a manner dictated by local
regulations.)
In the Laboratory
Apparatus
The experiment requires access to a stopped-flow spectrophotometer equipped with a suitable data acquisition
system. The reactions described here were followed using a
Durrum D110 instrument in conjunction with a Northstar
Horizon computer. The cell path length was 2.0 cm. Drive
syringes were thermostatted to 25.0 C. Olis software was
used for data acquisition and for the evaluation of rate constants (On Line Instrument Systems Inc., Bogart, GA
30622).
ln
[FeSCN]eq
[FeSCN]eq [FeSCN]
= k f [Fe]T + k r t
(1)
(2)
(3)
(4)
(5)
(6)
(8)
(9)
ln
A eq
A eq A
= k f [Fe]T + k r t
(10)
where Aeq represents the absorbance of the system at equilibrium. Equation 10 predicts that a plot of { ln(A eq A) versus t will be linear with slope (kf[Fe]T + kr). The latter quantity is defined as the observed first-order rate constant, kobs.
That is,
kobs = (k1 + k 2K a1/[H +])[Fe]T + k {1 + k{2Ka2 /[H+] (11)
Procedure and Results
It is generally best for students to work in pairs. They
should first prepare the three sets of iron(III) solutions described in Table 1.3 The reagents in series A are made up to
be 0.20 M in H+ concentration, while members of the B and
C series are 0.40 M and 0.60 M in [H+], respectively. Within
each series the iron(III) concentration varies over the same
range: ca. 0.005 to 0.04 M. Each solution is made up to a
volume of 10.00 cm3 and each contains sufficient NaClO4 to
maintain ionic strength at 1.00 M. This stage of the experiment generally takes 30 to 40 minutes to complete.
Before commencing the stopped-flow investigation it is
informative for students to gain a feeling for the rapidity of
the reaction they are about to examine. This can be achieved
through simple test tube experiments by mixing NaSCN solution (ca. 5 10{3 M) with an approximately equal volume
of acidified, dilute ferric ion solution. Even for concentrations of iron(III) down to 5 10{3 M the formation of the
thiocyanato complex appears to be instantaneous.
A thorough familiarity with the operation of the spectrophotometer flow system is also important. If the valves
controlling the transfer of reagents from reservoir to drive
syringes are opened in the wrong sequence premature mixing of the reagents may result. Such an occurrence will almost certainly require the preparation of replacement
solutions. A 10 cm3 volume of iron(III) solution is sufficient
to flush a drive syringe between runs, and is enough for
several replicate determinations.
The solutions of Table 1 are separately mixed in the
stopped-flow reactor with an equal volume of NaSCN solution (ca. 5 10{4 M ) and the complexation reaction is monitored at 450 nm. For best results the reactants should be
thermostatted in the drive syringes for at least 1 min before
initiating the reaction. The increase in absorbance is followed over five reaction half-lives (5 t 1/2) with the infinity
absorbance reading (i.e. Aeq) being recorded after at least
1215
In the Laboratory
Table 1. Stock Solution Volumes for Preparation of Iron(III)
Reagentsa
Solution
Designation
A1
0.25
1.90
3.85
A2
0.50
1.80
3.70
A3
1.00
1.60
3.40
A4
1.50
1.40
3.10
A5
2.00
1.20
2.80
B1
0.25
3.90
2.85
B2
0.50
3.80
2.70
B3
1.00
3.60
2.40
B4
1.50
3.40
2.10
B5
2.00
3.20
1.80
C1
0.25
5.90
1.85
C2
0.50
5.80
1.70
C3
1.00
5.60
1.40
C4
1.50
5.40
1.10
C5
2.00
5.20
0.80
[Fe]T
(M)
[H+]
(M)
k obs
(s{1)
k calcb
(s{1)
A1
0.00221
0.10
0.116
2.96
3.03
A2
0.00442
0.10
0.193
3.62
3.56
A3
0.00884
0.10
0.292
4.66
4.63
A4
0.0133
0.10
0.346
5.65
5.69
A5
0.0177
0.10
0.388
6.76
6.76
B1
0.00221
0.20
0.117
2.02
2.03
B2
0.00442
0.20
0.194
2.42
2.41
B3
0.00884
0.20
0.293
3.23
3.19
B4
0.0133
0.20
0.356
4.00
3.96
B5
0.0177
0.20
0.390
4.71
4.73
C1
0.00221
0.30
0.118
1.72
1.69
C2
0.00442
0.30
0.195
1.96
2.03
C3
0.00884
0.30
0.298
2.71
2.71
C4
0.0133
0.30
0.356
3.39
3.38
C5
0.0177
0.30
0.395
4.04
4.06
Duplicate data recorded for three or four runs allows reproducibility to be tested, but does not markedly extend the
time required.
Under the conditions employed in this study the
iron(III)thiocyanato product is never fully formed, with ca.
20% conversion at the lowest [Fe]T and 66% at the highest.
The approach to equilibrium is always first order, however,
irrespective of the difference between the initial and final
states. Table 2 gives A values and pseudo-first-order rate
constants (kobs ) obtained in a typical study.
Included in Table 2 are computed values of the firstorder rate constants, kcalc, obtained from a least squares fit
of the data to eq 11. This analysis uses literature values (8,
9) for Ka1 (2.04 10{3 M) and Ka2 (6.5 10{5 M), which give
best fit values4 of k1 =109(10) M {1s {1, k{1 = 0.79(0.10) s{1,
k2 = 8020(800) M{1s{1, and k{2 = 2630(230) s{1 . The kinetically
determined value of the formation constant for iron(III)
thiocyanate is therefore 109/0.79 M {1 = 138(29) M{1.
The absorbance data in Table 2 are treated with the
knowledge that [Fe(OH2)5 SCN]2+ is the only absorbing species present at equilibrium. If Alim represents the limiting
absorbance corresponding to the situation where all the
SCN{ is converted to [Fe(OH2 )5SCN]2+, then the concentration ratio [Fe(OH2)5SCN]2+ /[SCN{] is simply A/(Alim A).
Therefore, the expression for determining the formation
constant from the spectrophotometric data is
Kf =
A
[Fe]T A lim A
A =
10 t1/2. This requires data collection times ranging from 0.5
s (for solution A5) to 2.0 s (for solution C1), with each reaction having a post-collection delay time of up to 3 s prior to
recording Aeq. The change in absorbance observed on reaction is designated as the positive quantity, A. If the kinetic
data are stored directly onto diskette this phase of the
experiment usually requires about 5 min per estimation.
1216
(12)
A limK f [Fe]T
1 + K f [Fe]T
(13)
In the Laboratory
k1
(M-1s-1)
k {1
(s{1)
Kf
(M{1)
k2
(M{1s{1)
0.5
130 (40)
1.3(0.2) 104
2.6(0.2)
104
0.5
150 (50)
0.5
90 (5)
1.6 (0.2)
1.0
97 (3)
0.75 (0.03)
1.0
1.0
109 (10)
0.79 (0.10)
138 (29)
8.0(0.8) 103
1.0
112 (5)
56 (10)
129 (7)
134
9.6(0.5) 103
P-jump (7 )
Stopped-flow (4 )
Stopped-flow (3 )
Spectrophotometric (14 )
Stopped-flow, this work
Spectrophotometric, this work
Other Considerations
Literature Cited
1217