E26 QUESTIONS & DISCUSSION

1. According to the UV-Vis spectrum X, both HCrO

4
-
and CrO(O
2
)
2
absorb at 360nm.
Therefore, when the absorbance at this wavelength would include the absorbance of both
species. How would this affect the reaction rate determination? How can this be fixed?

Since the absorbance at 360nm would include both that of the reactant (Cr
7+
) and the product
(Cr
5+
), it would probably overestimate the reaction rate by making the disappearance rate
(decrease in absorbance) of HCrO
4
-
seem larger than it really is by including the appearance rate
(increase in absorbance) of CrO(O
2
)
2
. This problem can be fixed by using the other absorption
peak of Cr(V) at 580nm, a wavelength at which only Cr(V) absorbs:
A
380
= A[Cr(VII)] + A[Cr(V)]
A
580
= A[Cr(V)]
A
380
> A
580

A[Cr(VII)]=A
380
A
580

By subtracting the absorbance at 580nm from the absorbance at 380nm, the absorbance of Cr(VII)
can be determined.
2. When using the stopped-flow method to determine the rate constant and the spectrum
shows a first-order decay/growth, which method is more accurate? Why?
Usually, both methods (reaction rate determination using a first-order decay or first-order growth)
should be equally valid and accurate since (1/a[A])d[A]/dt = (1/b[B])d[B]/dt for a reaction
aAbB. In this experiment, however, one of the absorbances (A
380
) used in this experiment
includes both that of the reactant and the product, and H
2
O
2
is involved in the forward reaction.
H
2
O
2
is thermodynamically unstable and decomposes to H
2
O and O
2
, with the rate of
decomposition increasing with increasing temperature, pH, and concentration. In addition, many
transition metals also catalyze the decomposition of H
2
O
2.
Therefore, due to the instability of
H
2
O
2
and the fact that A
380
= A[Cr(VII)] + A[Cr(V)], the first-order decay should be used here.
SOURCE: N.N. Greenwood, A. Earnshaw (1997). Chemistry of the Elements (2nd ed.). Oxford UK:
Butterworth-Heinemann. A great description of properties & chemistry of H2O2.

3. In this experiment, which reactant has a larger impact on the reaction half life, H
+
or
H
2
O
2
? How does this affect the determination of the reaction mechanism?
HCrO
4
-
+ 2 H
2
O
2
+ H
+
CrO(O
2
)
2
H
2
O + 2 H
2
O
R = k[HCrO
4
-
]
m
[H
2
O
2
]
n
[H
+
]
o

=>

vial 15 vial 19 vial 20
H
2
O
2
600 L 500 L 600 L
1M HNO
3
300 L 400 L 400 L

290.7 331.4 375.7

The absorption spectrum for the product is used since only CrO(O
2
)
2
absorbs at this
wavelength, and no H
2
O
2
is involved in the backward reaction. Even though the reaction
orders m,n,o are still unknown, the reaction rate will always be proportional to k
obs
, the
reaction rate constant, regardless of the order of the reaction. The rate constants were
determined by fitting the experimentally obtained spectra were fitted with the exponential
function above to obtain k
obs
. Since the concentration of H
2
O
2
is the same in both vials 15 and
20, their ratio can be used to determine the reaction order of H
+
. Similarly, the concentration
of H+ is the same in vials 19 and 20 can their ratio can therefore be used to determine the
reaction order of H
2
O
2..
Thus,

Even though the reaction order for H
+
is slightly larger than that of H
2
O
2
, they are both
approximately equal to 1, which means that both have about the same impact on the reaction
half-time. This makes sense since slightly dilute acidic solutions are needed to ensure that
H
2
O
2
does not decompose and thus will be able to oxidize HCrO
4
-
to CrO(O
2
)
2
. In terms of
the reaction mechanism, this means that a reasonable reaction mechanism would have to
include both the participation of H+ and H
2
O
2
.







4. Please derive the relationship between [A] and time for n=0,1,2, where n= reaction
order.