Name: George Nogueira de Oliveira D14124795

Co-worker: Abiot Woldegeorgis

Date: 08/10/2014
Title of experiment: Kinetic Study of a Reversible Reaction
Abstract
In this report the forward and reverse rate constants and equilibrium constant are
measured. In this proposal, the hydration of 1,3-dichloropropanone is monitored by UVVisible spectrometer, as there is a decrease in absorbance of the carbonyl at 282 nm.
Experimental data were collect and the values obtained were compared with the data
from literature.

Introduction
A kinetic experiment consists of measuring the concentration of one or more reactants
or products at a number of different times during the reaction. Almost all the reaction
rates depend on the concentration of reactants, while for reversible reactions they are
also affected by those of products (ARNAUT, 2007).
In this experiment the kinetics of the reversible hydration of 1,3-dichloropropanone is
investigated, the reaction is shown below:

(ClCH 2 ) 2 CO=O

H2 O

kh

kd

(ClCH 2 )2 C ( OH )2

kh and kd are the rate constant for hydration (forward reaction) and dehydration
(reverve reaction) respectively.
For the purpose of determining ratio and equilibrium constants it is often experimentally
convenient the use of an analytical method that provides an instrumental signal that is
proportional to concentration. Solution absorbance, fluorescence intensity, and
conductance are examples of this type of instrument response (CONNORS, 1990).
Thus, the experiment was based on the fact that only 1,3-dichloropropane absorbs in
the UV-Visible while the product does not. Therefore the course of the reaction can be
monitored by the decrease of the carbonyl group at 282 nm (max) as a function of time.
The power to which the concentration of a species (a product or a reactant) is raised in
a reaction is expressed by the order of the reaction with respect to that species
(ATKINS, 2014). In this experiment the reverse reaction is first order, while the forward
reaction is pseudo-first order since the water is present in large excess. Consequently
the integrated rate law for a reversible first order reaction can be applied:

ln ( At - Ae ) =-k obs t + ln ( A0 - Ae )

(1)

At are the absorbance readings at various times and Ae is the absorbance reading
when the reaction has reached the equilibrium and

Kobs = K h + Kd

(2)

Hence plotting ln (At Ae) versus t a straight line with slope equal to Kobs is obtained.
(A0 Aeq) / Aeq = Kh / Kd = Kc

(3)

Once the values of kh + kd and kh / Kd means the individual values of kh and kd can be
calculated.

Results and Discussions

After all the experimental procedures were done the results obtained were tabulated
and organized in the the table below:
Table 1. Results from spectrum data of 1,3-dichloropropanone.

Aborbance in
the
equilibrium
(Ae)
1,2245

Time / s
0
10
20
30
40
50
60
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210
220
230
240
250
260
270
280
290
300
310
320
330
340
350
360

Absorbance / At
2,0038
1,9887
2,0286
2,0126
1,9886
1,9807
1,9733
1,9379
1,9808
1,9447
1,9247
1,925
1,9188
1,8987
1,912
1,8805
1,8989
1,8753
1,8521
1,8468
1,8099
1,8519
1,8149
1,8195
1,7999
1,7997
1,7711
1,7719
1,7668
1,7533
1,7446
1,7402
1,7274
1,7358
1,7272
1,7073
1,7104

(At - Ae)
0,7793
0,7642
0,8041
0,7881
0,7641
0,7562
0,7488
0,7134
0,7563
0,7202
0,7002
0,7005
0,6943
0,6742
0,6875
0,6560
0,6744
0,6508
0,6276
0,6223
0,5854
0,6274
0,5904
0,5950
0,5754
0,5752
0,5466
0,5474
0,5423
0,5288
0,5201
0,5157
0,5029
0,5113
0,5027
0,4828
0,4859

ln (At - Ae)
-0,2494
-0,2689
-0,2180
-0,2381
-0,2691
-0,2794
-0,2893
-0,3377
-0,2793
-0,3282
-0,3564
-0,3560
-0,3649
-0,3942
-0,3747
-0,4216
-0,3939
-0,4296
-0,4659
-0,4743
-0,5355
-0,4662
-0,5270
-0,5192
-0,5527
-0,5530
-0,6040
-0,6026
-0,6119
-0,6371
-0,6537
-0,6622
-0,6874
-0,6708
-0,6878
-0,7282
-0,7218

370
380
390
400
410
420
430
440
450
460
470
480
490
500
510
520
530
540
550
560
570
580
590
600
610
620
630
640
650
660
670
680
690
700
710
720
730
740
750
760
770
780
790
800
810
820

1,7031
1,6993
1,6797
1,6877
1,6835
1,6545
1,6474
1,6622
1,6549
1,6544
1,6302
1,6375
1,6237
1,6333
1,6175
1,6015
1,6138
1,592
1,5859
1,5889
1,5859
1,5798
1,5712
1,5624
1,5676
1,5652
1,5564
1,5453
1,5507
1,5345
1,54
1,5375
1,5266
1,5134
1,5213
1,5058
1,509
1,5058
1,5013
1,4964
1,4941
1,4771
1,4812
1,4767
1,4771
1,4697

0,4786
0,4748
0,4552
0,4632
0,4590
0,4300
0,4229
0,4377
0,4304
0,4299
0,4057
0,4130
0,3992
0,4088
0,3930
0,3770
0,3893
0,3675
0,3614
0,3644
0,3614
0,3553
0,3467
0,3379
0,3431
0,3407
0,3319
0,3208
0,3262
0,3100
0,3155
0,3130
0,3021
0,2889
0,2968
0,2813
0,2845
0,2813
0,2768
0,2719
0,2696
0,2526
0,2567
0,2522
0,2526
0,2452

-0,7369
-0,7449
-0,7870
-0,7696
-0,7787
-0,8440
-0,8606
-0,8262
-0,8430
-0,8442
-0,9021
-0,8843
-0,9183
-0,8945
-0,9339
-0,9755
-0,9434
-1,0010
-1,0178
-1,0095
-1,0178
-1,0348
-1,0593
-1,0850
-1,0697
-1,0768
-1,1029
-1,1369
-1,1202
-1,1712
-1,1536
-1,1616
-1,1970
-1,2417
-1,2147
-1,2683
-1,2570
-1,2683
-1,2845
-1,3023
-1,3108
-1,3759
-1,3598
-1,3775
-1,3759
-1,4057

830
840
850
860
870
880
890
900
910
920
930
940
950
960
970
980
990
1000
1010
1020
1030
1040
1050
1060
1070
1080
1090
1100
1110
1120
1130
1140
1150
1160
1170
1180
1190
1200
1210
1220
1230
1240
1250
1260
1270
1280

1,4685
1,4658
1,461
1,4653
1,4566
1,4436
1,4438
1,4388
1,4473
1,4299
1,424
1,4303
1,4264
1,4258
1,4194
1,4194
1,4055
1,4069
1,4033
1,3978
1,4039
1,3994
1,3919
1,3959
1,3938
1,3804
1,3841
1,3823
1,3746
1,3761
1,3672
1,3772
1,3675
1,3709
1,3652
1,3616
1,3621
1,3565
1,357
1,3585
1,3547
1,3551
1,3445
1,3475
1,3441
1,336

0,2440
0,2413
0,2365
0,2408
0,2321
0,2191
0,2193
0,2143
0,2228
0,2054
0,1995
0,2058
0,2019
0,2013
0,1949
0,1949
0,1810
0,1824
0,1788
0,1733
0,1794
0,1749
0,1674
0,1714
0,1693
0,1559
0,1596
0,1578
0,1501
0,1516
0,1427
0,1527
0,1430
0,1464
0,1407
0,1371
0,1376
0,1320
0,1325
0,1340
0,1302
0,1306
0,1200
0,1230
0,1196
0,1115

-1,4106
-1,4217
-1,4418
-1,4238
-1,4606
-1,5182
-1,5173
-1,5404
-1,5015
-1,5828
-1,6119
-1,5809
-1,6000
-1,6030
-1,6353
-1,6353
-1,7093
-1,7016
-1,7215
-1,7527
-1,7181
-1,7435
-1,7874
-1,7638
-1,7761
-1,8585
-1,8351
-1,8464
-1,8965
-1,8865
-1,9470
-1,8793
-1,9449
-1,9214
-1,9611
-1,9870
-1,9834
-2,0250
-2,0212
-2,0099
-2,0387
-2,0356
-2,1203
-2,0956
-2,1236
-2,1937

1290
1300
1310
1320
1330
1340
1350
1360
1370
1380
1390
1400
1410
1420
1430
1440
1450
1460
1470
1480

1,3394
1,3396
1,3465
1,3378
1,3308
1,3378
1,3326
1,3309
1,3241
1,3192
1,3253
1,3221
1,3125
1,314
1,3188
1,3206
1,317
1,3145
1,3097
1,3077

0,1149
0,1151
0,1220
0,1133
0,1063
0,1133
0,1081
0,1064
0,0996
0,0947
0,1008
0,0976
0,0880
0,0895
0,0943
0,0961
0,0925
0,0900
0,0852
0,0832

-2,1637
-2,1620
-2,1037
-2,1777
-2,2415
-2,1777
-2,2247
-2,2405
-2,3066
-2,3570
-2,2946
-2,3269
-2,4304
-2,4135
-2,3613
-2,3424
-2,3805
-2,4079
-2,4628
-2,4865

The spectrum shows the forward reaction of dehydration of 1,3-Dichloropropane.

According to the spectra data the value of absorbance (A e) when the reaction reached
the equilibrium is 1.2245.

Figure 1. Spectrum of dehydration of 1,3-dichloropropanone at 25 C.

Reaction followed spectrophotometrically at 282 nm.

Dehydration of 1,3-Dichloropropanone
2.10
1.90
1.70
Absorbance / Ae

1.50
1.30
1.10
0

500 1000 1500 2000 2500 3000

Time / s

Also, it was plotted a graphic of ln (At Ae) versus t, which yielded a straight line with
slope (Kobs) equal to 2.0 x 10-3 and the standard deviation (2) was 0.66.
0.00
0
-0.50

200
400
600
f(x) = - 0x - 0.18
R = 1

800

1000

1200

1400

-1.00
ln (At - Ae)
-1.50
-2.00
-2.50
t/s

Figure 2. Pseudo-first order plot of the hydrolisis of 1,3-dichloropropanone at 25 C.

Reaction followed spectrophotometrically at 298 nm.

The information found allowed the calculation of Kh, Kd and Kc. Then the values were
compared with the one the literature value given in the reference material. The value of
Kc was calculated according the equation bellow:

(A0 - Ae )
= kc
Ae

(4)

Where A0 is the absorbance of the reagent at the beginning of reaction, Ae is the

absorbance in the equilibrium. It was found value of kc = 0.636 closer to the value found
in the literature, where kc = 0.658. Knowing the value of kc, it is possible to calculate the
dehydration constant and hydration constant:

Kobs = Kh + Kd = 2.0 x 10-3

(2)

Knowing that kc = kh / kd, we have:

Kc = K h / Kd = 0.658

(5)

K h = 0.658 K d
0,658 Kd + Kd = 2.0 x 10-3
Kd =

2.0 x 10
1.658

-3

Kd = 1.206 x 10-3 s-1

Finally it is possible to calculate the value of Kh:
Kh = 0.658 Kd
Kh = 7.93 x 10-4 s-1
Even though the values found are higher than the ones presented in the literature,
there are some aspects related to the experimental procedures to regard, such as
temperature of solution, and certification of the beginning of the reaction. Moreover, the
rate of reaction depends on the temperature at which occurs. When the temperature
increases the reaction rate increases as well. The reagents species require a minimum
amount of energy present at the time the reactants collide in the reaction step, which is
called activation energy.
Conclusion
With all procedure experiment done, it is possible to conclude that that the forward and
reverse rate constants (Kh and Kd) and equilibrium constant (Kc) for 1,3Dicholoropropanone was determined. Also, the concentration of reagents monitored by

reversible first order kinetics and forward pseudo-first order kinetics drop from an initial
concentration exponentially with time.
Bibliography
ARNAUT, L; FORMOSINHO, S; BURROWS, H. Chemical Kinetics: From Molecular
Structure to Chemical Reactivity. Elsevier Oxford, 2007.
ATKINS, P. W. Physical Chemistry. Oxford : Oxford University Press, 2014
CONNORS, K. A. Chemical Kinetics: the study of reaction rates in solution. VHC
Publishers - New York, 1990.
O. A. EL SEOUD, S. ROPKE and P. T. A. Sumodjo, Education in Chemistry, pg. 105106.