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NAME: Andrew Grant NAME: DATE: Monday 3RDSeptember 2012

Lab Day: Monday Week 1 Experiment 2

Experiment 2: Kinetics of 2-Chloro-2-methylpropane HYDROLYSIS BY CONDUCTIVITY THEORY: The solvolysis of the tertiary butyl halides in water takes place by an SN1-mechanism . The reaction is unimolecular - only one species is involved in the slow step of the reaction. The reaction rate depends only on the concentration of the alkyl halide (C4H9Cl), not the nucleophile: R = k [C4H9Cl]. In an SN1 reaction the key step is the loss of the leaving group to form the intermediate carbocation. This step is the slow, rate determining step of the reaction. The carbocation is then attacked by a nucleophile in a fast second step to form the product. The more stable the carbocation is, the easier it is to form, and the faster the SN1 reaction will be. The planar, trigonal carbocation may be attacked equally well from either side by a nucleophile. As a consequence, an SN1 reaction leads to a racemization, in which both retention and inversion of configuration at a chiral center occur to the same extent. Optically active tertiary haloalkanes produce a mixture of two enantiomers (mirror image isomers).

Hence the hydrolysis of t-butyl chloride can be monitored by following the change in conductance of the reaction mixture with time. By determining the conductivity as a function of
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time, the rate constant can be found. If the reaction is carried out at different temperatures, the activation energy can also be found. C4H9Cl + 2H2O C4H9OH + H3O+ + Cl-

With respect to the above equation, there is an increase in conductivity of the solution as the reaction continues due to the formation of hydroxonium and chloride ions. PROCEDURE: Note: ONLY 2-Chloro-2-methylpropane was used. The influence of initial concentration part of the experiment was conducted at 38 0 C. RESULTS: For lnt-t+vs time the data was split into t and t + . In order to do this, the time used for each data set was divided into two sets. The first set, , consisted of the corresponding conductivities of the first half of the time values and the second set, t + , consisted of the second set of the conductivities. Therefore, ,for the concentration part of the experiment corresponding conductivities for times 30 seconds to 600 seconds were t values. While, those conductivities for time 630 seconds to 1200 seconds were t + values. Table 1. values for graph 1: lnt-t+vs time for 0.1mL alkyl halide at 38 0 C Time/s 30 60 90 120 150 180 210 240 t-t+/s 187 216 224 232 240 250 260 272 lnt-t+s 5.23 5.37 5.41 5.44 5.48 5.52 5.56 5.61
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270 300 330 360 390 420 450 480 510 540 570 600

282 290 300 310 320 330 342 352 360 368 376 385

5.64 5.67 5.70 5.74 5.77 5.80 5.83 5.86 5.89 5.91 5.93 5.95

Table 2. values for graph 1: lnt-t+vs time for 0.15mL alkyl halide at 38 0 C. Time/s 30 60 90 120 150 180 210 240 270 300 330 360 t-t+/s 90.7 130.9 140.9 154.9 168.2 179.6 188.1 205 224 247 271 283 lnt-t+s 4.51 4.87 4.95 5.04 5.125 5.19 5.24 5.32 5.41 5.51 5.60 5.64

390 420 450 480 510 540 570 600

305 322 338 354 376 388 402 416

5.72 5.77 5.82 5.87 5.93 5.96 6.00 6.03

Table 3. Values for graph 1: lnt-t+vs time for 0.20mL alkyl halide at 38 0 C. Time/s 30 60 90 120 150 180 210 240 270 300 330 360 390 420 450 403 412 420 432 445 456 469 480 506 518 530 542 552 566 578 t-t+/s 6.0 6.02 6.04 6.06 6.09 6.12 6.15 6.17 6.23 6.24 6.27 6.30 6.31 6.33 6.36 lnt-t+s

480 510 540 570 600

590 600 624 634 646

6.38 6.39 6.44 6.45 6.47

For temperatures corresponding conductivities for times 20 seconds to 240 seconds were t values. While, those conductivities for time 260 seconds to 480 seconds were t + values. Table 4 : showing values for plotting graph 5: lnt-t + vs time at 40 0 C t/s t + /s t-t + s lnt-t + s 4930 10680 5750 8.657 5350 11320 5970 8.695 5820 11940 6120 8.719 6320 12390 6070 8.711 6870 12870 6000 8.700 7140 13380 6240 8.739 7600 14000 6400 8.764 8200 14730 6530 8.784 8540 15500 6960 8.848 9390 15940 6550 8.787 9700 16290 6590 8.793 10100 16800 6700 8.900 Table 5 : showing values for plotting graph 6: lnt-t + vs time at 45 0 C. t/s 3970 4180 4200 4290 4370 4450 4520 4600 4680 4760 4830 4900 t + /s 5000 5070 5140 5220 5310 5390 5450 5500 5580 5660 5730 5800 t-t + s 1030 890 940 930 940 940 930 900 900 900 900 900 lnt-t + s 6.937. 6.791 6.846 6.835 6.845 6.845 6.835 6.802 6.802 6.802 6.802 6.802 t/seconds 20 40 60 80 100 120 140 160 180 200 220 240

t/seconds 20 40 60 80 100 120 140 160 180 200 220 240


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Table 6 showing values for plotting graph 7: lnt-t + vs time at 49 0 C. t/s 448 560 644 767 879 989 1103 1233 1348 1471 1599 1721 CALCULATIONS: 1. Using conductivity values at 30s and 630s for a volume of 0.10mL of alkyl halide were = 600s: t-t + = 206 - 393s = 187 s ln (187) = 5.23 This was also done for 0.15 and 0.20mL of alky halide. 2. Calculation of gradients: Gradient = Change in t-t + Change in time /(s) It follows that from the equation, lnt-t + = -kt + constant so that the gradient = -k From graph 2:ln t-t + vstime/s for 0.10 mL of alkyl halide: Gradient = y/x = -9.88833- (-8.40057)/600-30 sec = 0.00261 Therefore k = 0.003 s-1 (to 3 d.p) From graph 3:ln t-t + vstime/s for 0.15 mL of alkyl halide:
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t + /s 1850 1982 2230 2380 2520 2660 2800 2960 3000 3210 3390 3480

t-t + s 1402 1422 1586 1613 1641 1671 1697 1727 1652 1739 1791 1759

lnt-t + s 7.246 7.260 7.370 7.386 7.403 7.421 7.437 7.454 7.409 7.461 7.491 7.473

t/seconds 20 40 60 80 100 120 140 160 180 200 220 240

Gradient = y/x = -9.6049 (-7.5199)/600-60 sec = 0.00311 Therefore k = 0.003 s-1 (to 3 d.p) From graph 4: ln t-t + vstime/s for 0.20 mL of alkyl halide: Gradient = y/x = -10.9351- (-9.70815)/600-150 = 0.00272 Therefore k = 0.003 s-1 (to 3 d.p).

From graph 5: lnt t + vs time/ seconds at 38 o C: Gradient = y/x = 8.90-8.657/240-20 = 0.00110 Therefore k = 0.00110 s -1

From graph 6: lnt t + vs time/ seconds at 45 o C: Gradient = y/x = 6.802-6.937/240-20 = 0.000614 Therefore k = 0.000614 s -1

From graph 7: lnt t + vs time/ seconds at 49 o C: Gradient = y/x = 7.473 7.246/ 240-20 = 0.001032 Therefore k = 0.001032 s-1 Calculating ln K for the temperature graphs in order to plot Graph 7: ln K vs 1/T: From graph 5: lnt t + vs time/ seconds at 38 o C:
K = 0.00110 s
-1

Therefore ln k = -6.812 (no units) From graph 6: lnt t + vs time/ seconds at 45 o C:


K = 0.000614 s -1

Therefore ln k = -7.395 (no units)


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From graph 7: lnt t + vs time/ seconds at 49 o C: K = 0.001032 s-1 Therefore ln k = -6.876 Calculating 1/T where T is in Kelvins: For 38 0 C: 273 + 38 = 311 K Therefore 1/T = 1/311 = 0.003215 K -1 For 45 0 C: 273 + 45 = 318 K Therefore 1/T = 1/ 318 = 0.003144 K -1 For 49 0C : 273 + 49 = 322 K Therefore 1/T = 1/322 = 0.003106 K -1 Table 7 showing values of graph 8 :ln K vs 1/T T/C 0 38 45 49 T/K 311 318 322 1/T in K-1 0.003215 0.003144 0.003106 k 0.00110 s -1 0.000614 s -1 0.001032 sln k -6.8124 -7.3955 -6.8763

Calculating value C from graph 8 :ln K vs 1/T: y=mx+c y = 586.24x + c In order to find c, substitute a set of values at pt (0.003215, -6.8124) -6.8124 = 586.24 (0.003215) + c -6.8124 = 1.885 + c C = -6.8124 -1.885 = -8.6974
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Therefore y = 586.24 x 8.6974 Necessary constants: R = 8.314 JK-1 mol-1 h = 6.626 x 10 -23 JK -1 kB = 1.38 x 10 -23JK -1 ln k1 = ln A Ea/RT is in the form y = c + mx

Calculating the value of A: ln A = -8.6974 A A = e-8.6974 = 1.67 x 10 -4 s-1

Note that Ea has units of energy and RT also has units of energy, so the exponential is a dimensionless quantity. This means that A has the same units as k. Calculating the value of Ea: Ea/R = 586.24 Ea/ 8.314 = 586.24 Ea = 586.24 x 8.314 Ea = 4873.999 Jmol-1 Ea = 4.87 KJ mol-1 Calculating the value of S : S /R = ln A In (kB T/h) -1 Let T be an average of three temperatures in K:

T = 311 + 318 + 322/3 = 317 K S = {ln A In ( kB T/h) -1 }R S = { -8.6974 In ( 1.381 x 10 -23 x 317)} x 8.314 (6.626 x 10 -34) S = 5.88 x 10 35 Jmol-1 K-1

Calculation for graph 2: ln ( t-t1+ ) ln (1/90.7 -1/130.9) = -5.688124306 NB: Graph 2- 5 followed the same sample calculation in order to obtain the y- values x- values were derived from time taken to conduct the experiment.

Graph 1 showing kinetics of different conc of alkylhalide vs time


7 6.8 6.6 6.4 At-t+ /s 6.2 6 5.8 5.6 5.4 5.2 5 0 100 200 300 400 500 600 700 Time in seconds y = 0.0009x + 5.9719 Series1 y = 0.0024x + 4.7239 y = 0.0011x + 5.3197 Series2 Series3 Linear (Series1) Linear (Series2) Linear (Series3)

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Graph 2 showing values for lnt-t+s vs time for 0.1mL of reactant


0 0 100 200 300 400 500 600 700

-2

-4

Series1 lnt-t+s -6 Series2 Linear (Series1)

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-10

y = -0.0042x - 7.4476

-12

Time seconds

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Graph 3 showing values for lnt-t+s vs time for 0.15 mL of reactant


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l n 0 0
t

100

200

300

400

500

600

700 Series1 Linear (Series1) Linear (Series1)

t +

-5 s y = -0.0007x - 7.1579

-10

-15 Time in seconds

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Graph 4 showing values for lnt-t+s vs time for 0.2 mL of reactant


-9.4 0 -9.6 100 200 300 400 500 600 700

-9.8

-10

-10.2 lnt-t+s -10.4 Series1 Linear (Series1)

-10.6 y = -0.0019x - 9.5495 -10.8

-11

-11.2

Time in seconds

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graph 5: ln t-t + vs time at 38 0 C


8.95

8.9

8.85

y = 0.0009x + 8.6446

8.8

ln t-t + 8.75

Series1 Linear (Series1)

8.7

8.65

8.6 0 50 100 150 Time in seconds 200 250 300

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Graph 6: ln t-t + vs time at 45 0 C.


6.96

6.94

6.92

6.9

6.88 ln t-t + 6.86

Series1 Linear (Series1)

6.84

6.82

6.8 y = -0.0003x + 6.8741 6.78 0 50 100 150 Time seconds 200 250 300

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Graph 7: ln t- + vs time at 49 0 C
7.55

7.5

y = 0.001x + 7.276

7.45

7.4

ln t-t + 7.35

Series1 Linear (Series1)

7.3

7.25

7.2 0 50 100 150 Time in seconds 200 250 300

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Graph 8 ln K vs 1/T
-6.8 0.0031 0.00312 0.00314 0.00316 0.00318 0.0032 0.00322 0.00324

-6.81 y = 586.24x - 8.6972

-6.82

-6.83

ln k -6.84

Series1 Linear (Series1)

-6.85

-6.86

-6.87

-6.88

1/T

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Discussion and Conclusion: The kinetics of 2-chloro-2-methylpropane was investigated using hydrolysis by conductivity method. This method was conducted in two ways: by changing the initial concentrations of the reactant which was the alkyl halide and secondly by changing the temperature. To determine the influence of initial concentration of the alkyl halide, the experimental procedure was repeated by varying the concentrations (i.e. 0.10 mL, 0.15 mL, and 0.20 mL) of the reactant in 25 mL of solvent (80 percent ethanol in water) while the temperature remained constant at 38 0 C. The results showed the effect on changes in concentration with time with respect to rate of reaction. Most chemical reactions proceed faster if the concentration of one or more reactants increased, in this experiment the reactant (alkyl halide) was increased as previously stated above. As concentration increases, the frequency with which the reactant molecules collide increases, leading to increased reaction rate. For example, the measured conductivity (t-t + s ) was increased from 90 , 187, and 403 when the concentration of the alkyl halide was increased from 0.10, 0.15 and 2.0 mL respectively. Additionally, tert, butyl halides undergo solvolysis in aqueous solvents, on this basis, conductometric measurement of the rate of formation of the hydrogen halide indicated the course of the reaction (meaning when concentration alkyl halide increased the formation of the hydrogen halide increased proportionately resulting in increased measured conductivity). Also by determining the conductivity as a function of time, the rate constant was found.After plotting a graph of lnt-t
+ svs

Time/s for 0.10, 0.15, and 0.20 mL of alkyl halide, the slope was found. Since the

equation lnt-t + = -kt + constant follows the y= mx + c, where m is the gradient, then the slope = -k. K was found to be 0.003 s-1 for all three concentrations employed. It was therefore ascertained, that the rate constant was not affected by the variation in concentrations. To determine the influence of temperature, the experimental procedure was repeated at varied temperature, while the concentration remained constant.The temperature was varied at 38, 45, and 49 0 C and a graph of lnt-t + vs time was plotted for each respective temperature. The value for k was determined to be as follows: 0.00110, 0.000614, 0.0010325 s -1 for each temperature respectively. In turn these values were used to plot graph 8: lnt-t + vs 1/T,
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which had an equation of y = 586.24x 8.6972. The graph confirmed that the hydrolysis of 2iodo-2-methlypropane was a first order reaction since k could be determined the equation lnt-t + vs time. By using the equation,lnt-t + vs 1/T, the pre-exponential factor A was found to be 1.67 x 10 -4 s-1, Ea = 4.81 KJmol-1 and S = 5.88 x 10 35 Jmol-1. The literature values for the reactant stated however, that Ea should be approximately 89.2 KJ mol -1 and S is approximately 15 Jmol-1. The disparity of results could be attributed to inaccurate results obtained when the experiment was conducted, due to poor technique in carrying out the experiment, and faulty conductivity meters which were shutting off sporadically during the experiment. As temperature increases, the reaction rate increases. This was described by the collision model, which stated that on the basis of kinetic molecular theory, molecules must collide to react. The greater number of collisions occurring per second, the greater the reaction rate and as the concentration of reactant molecule increases, the number of collisions increases, leading to an increase in reaction rate. Also when molecules collide, they must be in the same orientation in order for a reaction to occur. When sufficient kinetic energy was obtained to change the potential energy of the molecule, this minimum energy called the activation energy was needed to initiate a chemical reaction. As a result, as demonstrated in the Arrehenius equation k = Ae-Ea/RT only temperature changes the rate constant k. Entropy (S) is a thermodynamic state function which measure quantitatively the amount of disorder present in the system. Since S was positive the system was marked as disordered. This was expected because since the temperature was increased in the second half of the experiment, entropy increases. Other factors that influence entropy and as of consequence reaction rates were the physical state of the reactants. Reactants must come together in order to react. The more readily molecules collide with each other, the more rapidly the react. In this experiment, since the reactant was homogenous i.e. in liquid solution/state, entropy of the system would increase because the reactant and solvent was in the same physical state.

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References: Brown,Theodor et al.Chemistry The Central Science tenth edition:NJ Pearson Prince Hall. http://www.uni-regenburg.de/Fakultaeten/nat_Fak_IV/Organische_Chemie/Didaktik/Ke

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