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FOCUS 7 Online Cumulative Example

You are working in a water treatment facility and want to measure the concentration of
iron(II) ions in the water supply. Iron(II) reacts with 1,10-phenanthroline (phen,1) to
form the deep red complex ion ferroin, Fe(phen)321, which can be used to determine its
concentration by spectrophotometry. However, in acidic solutions the complex decom-
poses in the following overall reaction, N N
Fe(phen) 321(aq) 1 3 H3O1(aq) ¡ Fe21(aq) 1 3 Hphen1(aq) 1 3 H2O(l) 1 1,10-Phenanthroline
To know how fast the concentration of the complex changes at different temperatures,
you first need to determine the activation energy of the reaction.
(a) The data in the following table were collected at 40 8C. Use these data to determine
the reaction order with respect to Fe(phen)321 and H3O1. (b) Identify the rate law for
the reaction and determine the value of the rate constant kr at 40 8C.
[Fe(phen)321]/ [H3O1]/ Initial rate/
Experiment (mol?L21) (mol?L21) (mol?L21?s−1)
1 7.5 3 1023 0.5 9.0 3 1026
2 7.5 3 1023 0.05 9.0 3 1026
3 3.75 3 1022 0.05 4.5 3 1025

(c) Use the rate constant from part (b) and the data in the following table to determine
the activation energy for this reaction. (d) How long would it take for the concentra-
tion of Fe(phen)321 to decrease by half at 25 8C?
Temperature/8C 506070
Rate constant, kr/s21 5.4 3 1023 2.2 3 1022 8.5 3 1022

PLAN
(a) Compare initial rates of reaction for pairs of experiments in the first table in which
only one reactant concentration is different. If the reactant concentration changes by
a factor f, the rate of reaction will change by a factor f a, where a is the order of reaction
with respect to that reactant.
(b) Substitute data from one experiment in the first table into the rate law and solve for
the rate constant, kr.
(c) Construct an Arrhenius plot, and from the slope, which is equal to 2Ea/R, find the
activation energy.
(d) Use Eq. 2 of Topic 7D, ln(kr2/kr1) 5 (Ea/R)(1/T1 2 1/T2), to calculate the rate con-
stant at 25 8C. Because the time required for the molar concentration to decrease by
half is the half-life of the reaction, consult Table 7B.1 to find the appropriate expression
to use to determine the half-life.
SOLVE
(a) Order in Fe(phen)321: Compare experiments 1 and 3. 50
Initial rate /(mmol·L–1·s–1)

In experiments 1 and 3, the molar concentration of Fe(phen)321

×3
is changed by a factor of 3 ( f 5 3) and the molar concentration 25

of H3O1 is held constant. Because the rate of reaction increases ×3

by a factor of 3, f a 5 3a 5 3, and so a 5 1. Therefore the 0
reaction is first order in Fe(phen)321. 0 0.02 0.04
[Fe(phen)32+] /(mmol·L–1)

Order in H3O1: Compare experiments 1 and 2. 50

Initial rate /(mmol·L–1·s–1)

In experiments 1 and 2 the molar concentration of H3O1 is

changed by a factor of 10 (f 5 10) and the molar concentration 25

of Fe(phen)321 is held constant. Because the rate of reaction ×10

stays the same, f a 5 10a 5 1, and so a 5 0. Therefore the reaction 0 1
is zeroth order in H3O1. 0 0.25
[H3O+] /(mol·L–1)
0.5
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2 Focus 7 Online Cumulative Example

(b) Write the rate law.

From the results of part (a) the rate law is

Rate of reaction 5 kr 3 Fe(phen) 321 4

Substitute the data from experiment 1 into the rate law and determine kr.
initial rate
644444474444448
9.0 3 1026 mol?L21?s21
kr 5 5 1.2 3 1023 s21
7.5 3 1023 mol?L21
14444444244444443
[Fe(phen)32⫹]

(c) Calculate the slope of the Arrhenius plot by using the data in 0
the second table and the rate constant at 40 8C. Use a graphing
calculator or other linear regression tool.

ln kr
–4
Slope 5 21.52 3 104 K

–8
2.9 3.1 3.3
1/(T/K) × 103

Because the slope is equal to 2Ea/R, from Ea 5 2R 3 slope,

Ea 5 2(8.3145 J?K 21?mol 21) 3 (21.52 3 104 K)

5 1.27 3 103 J?mol21 5 127 kJ?mol21

(d) From ln(kr2/kr1) 5 (Ea/R)(1/T1 2 1/T2), using points at 25 8C

and 40 8C,
313 K

kr2 1.27 3 105 J?mol21 1 1

ln kr
ln 5 3a 2 b
kr1 8.3145 J?K21?mol21 313 K 298 K
5 22.45p 298 K

1/(T/K)

From x 5 eln x and because kr1 5 1.2 3 1023 s21,

Rate constant, kr 313 K
kr2
5 e 22.45p 1.2 × 10–3 s–1
kr1
kr2 5 (1.2 3 10 23 s 21 ) 3 e 22.45p 298 K
1.0 × 10–4 s–1
5 1.0 3 10 24 s 21
Temperature, T/K

The expression for the half-life of a first-order reaction from

Table 7B.1 is t1/2 5 (ln 2)/kr.
Concentration

ln 2 1.9 h
t1/2 5
1.0 3 1024 s21
5 6.9 3 103 s 5 1.9 h
Time, t/h