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Experiment 3: Kinetics of nucleophilic substitutions


The purpose of this experiment is to understand the kinetics of the hydrolysis of t-butyl chloride. The kinetic order of reaction was studied under the effects of variations in temperature, solvent polarity, and structure. It is particularly observed in tertiary halides i.e. in SN1 mechanism, Nucleophilic Substitution which is in 1st order. It is basically a reaction that involves substitution by a solvent that pretends like a nucleophile i.e. it donates electrons. The reaction being in first order means the rate of the reaction depends on the concentration of only one reactant. Following is the reaction for t-butyl chloride in water:

The rate determining step determines the order of reaction hence, the carbocation formed during the process does so. Order of reaction is the power to which the concentration of the reactant is raised to in a rate expression whereas the rate constant, k, is a constant that changes with respect to change in concentration of the reactants. Arrhenius plot i.e. ln k versus 1/Temperature, aids in determining the activation energy required in the reaction. Arrhenius equation states how rate constants vary with temperature and activation energy. It is basically: lnk= -EaRT+lnA , where k is rate constant, Ea is the activation energy in Joules/mol, R is the gas constant, T is temperature in Kelvin and A is frequency factor or pre-exponential factor. Results: Upon addition of bromophenol blue indicator, the solution changed its transperant color to blue and once t-Butyl chloride was added, following the reaction, the color changed to yellow in all the cases except for variation in substrate. I-A Variation of hydroxide concentration Table 1: variation in k values for variation in hydroxide concentration % completion 10 20 30 Time (seconds) 59 116 269 K 0.001786 0.000908 0.000393

The rate constant does not change significantly as time increases for every 10% increment in the completion of t-Butyl chloride concentration.

I-B Variation of t-Butyl Choride concentration Table 2: Data for various techniques used to prove that this reaction is first order reaction
[tbutCl] 0.06 0.03 0.015 1/[t-Butyl] 16.66667 33.33333 66.66667 Ln[t-Butyl] -2.8134107 -3.5065579 -4.1997051 Time 30 60 92

Figure 1: relationship between [t-Butyl] and time is shown in the above graph which is not linear.

Figure 2: Relationship between ln [t-Butyl] and time is linear and the R2 value supports the first order reaction

Figure 3: Relationship of 1/[t-Butyl] and time is not linear as shown in the above graph.

II Study of temperature variation Table 3: Summary of average activation energy determined from ln k and log k vs. 1/T graphs Temperature (K) 284 294 304 -log k Ln k -8.3814 3.639993 -6.32772 2.748096 -4.95601 2.151401 Average Ea Order of reaction Error estimate 0.231 = 23.1%

123.13kJ/mol First order

Figure 4: Arrhenius plot: ln k vs. 1/Temperature (K-1)

Figure 5: Relationship of log k and 1/temperature (K-1) shows a positive slope that determines the activation energy

Figure 6: Reaction-energy diagram of substitution of chlorine atom from tertiary-Butyl chloride (RX) by hydroxide ion from sodium hydroxide (OH- being the nucleophile) in polar protic solvent in SN1 reaction. III. Study of solvent polarity Initially 70% water 30% acetone was used for the previous parts of the experiment, but the dilution factor was varied for the trials for this part. The higher the concentration of water, the faster did the reaction occur. For experiment IV: Study of structural variations in substrate, when isopropyl chloride was used, no reaction was observed when kept for almost 5 minutes and 24 seconds at room temperature nor when heated for other 2 minutes and 23 seconds. Discussion: Nucleophilic substitution reaction is of two types SN1 and SN2. SN1 is a unimolecular reaction that involves a strong leaving group and a good nucleophile and this occurs in two steps. The first step is the formation of carbocation on the tertiary carbon compound after the leaving group has left the carbon compound independently. This is the rate determining step and the attack of a nucleophile is a fast step whereas in SN2, a one-step reaction that involves a backside attacks of a nucleophile on a primary or secondary carbon compound. In this experiment, tertiary-butyl chloride was used to react with sodium hydroxide in order to display a two-step mechanism SN1 since chlorine is a better leaving group and hydroxide ion is a good nucleophile. The carbocation formed when chlorine ion leaves the compound is attracted to the hydroxyl nucleophile forming t-Butanol. In part I-A, the hydroxide concentration was varied but no change in rate constant. This was observed when the rate constants were determined using the logarithmic relationships with

percent reaction. This result explains the fact that the reaction rate is independent of hydroxide concentration. In part I-B, the t-Butyl chloride concentration was varied and it was observed according to the graphs shown in results section (figure 1,2, & 3) that the reaction was dependent on the change in t-Butyl chloride concentration. With the change in time by an increment of 30 seconds, the ln of concentration increased in a linear fashion, proving that this is a first order reaction. First order reaction means reaction rate is proportional to the concentration of a single reactant raised to the first power. In part II, the temperature was varied for the same t-butyl chloride and sodium hydroxide concentration, distilled water and water-acetone mixture that was used in trial one of part I-A. As the temperature was decreased by 10oC from room temperature, the time taken by the reaction to complete increased and as the temperature was increased by 10oC from the room temperature, the time elapsed for the reaction to complete decreased. Temperature played a catalytic role in this experiment; as such it did not bring any change to the intermediate forming or to the substrate. Nevertheless, Arrhenius plot, which is a graph showing the relationship between ln k and 1/temperature (oK-1), that helps in determining the activation energy needed for the intermediates to form from the slope of the graph (figure 4 & 5). The activation energy was determined to be 123.2kJ/mol. The activation energy determined from the log k vs. 1/T graph was 123.1kJ/mol. The reaction-energy diagram of the SN1 reaction, Figure (6), shows whether the rate depends on the strength or the concentration of the nucleophile. The ionization step, i.e. the rate determining process (first step), is highly endothermic, and its large activation energy determines the overall rate of reaction. The nucleophilic attack is strongly exothermic, with a lower-energy transition state. In effect, a nucleophile reacts with the carbocation almost as soon as it forms. In part III, different concentrated water-acetone mixture was used in order to determine the solvent polarity. The more polar the solvent, the faster is the nucleophilic substitution reaction (SN1) because polar solvents surround the carbocation that has an effect of stabilizing the intermediate and also polar protic solvents, the solvents that can easily donate protons, prevent a recombination of carbocation with the leaving group due to presence of a hydrogen atom bonded with a strong electronegative element. In part IV, a different substrate was used to observe the activity of the reaction. Isopropyl chloride, a secondary carbon, is less sterically hindered. For SN1 to occur, the nucleophile attacks the intermediate i.e. the carbocation and not the substrate, and this carbocation is formed after the leaving group leaves. A stable carbocation is at the most substituted carbon, which in this case for isopropyl carbocation would be at a secondary carbon, less substituted than a tertiary carbon. This carbocation would be unstable because ionized higher-order carbons are stabilized by hyperconjugation but unsubstituted carbons are not, i.e. electrons from sigma bonds interact with an adjacent empty or partial empty non-bonding or anti-bonding p-orbital for a stable molecule. Hence, no reaction was observed under any condition when isopropyl chloride mixture was kept idle for 5 minutes and 24 seconds and then heated till 7 minutes 47 seconds. Questions:

1. How would the Ea value measured in acetone compare with that measured in H2O? Explain. Ea value measured in acetone would be a lot higher than that of measured in water because water is a polar protic solvent and it supports unimolecular nucleophilic substitution to occur in it since it has a proton to donate to the leaving group that leaves from the substrate whereas in acetone, it is harder to get a proton to protonate the leaving group. In acetone, CH3COOH, it is easier for the hydroxide ion (OH-) to leave rather than H+ since the molecule would not be stable if a hydrogen atom left. The leaving of hydrogen atom implifies that it would satisfy the leaving group and it would leave only if the molecule would be stable enough. In addition to SN1 reaction, in the rate determining step, two ions are formed and for the solvolysis for these ions, and for lowering their activation energy to form those, polar protic solvents are used and water fulfills the requirement. Also, strong solvation may weaken the strength of the nucleophile because of the energy needed to remove from the solvent molecules and water again fulfills this. Hence, activation energy measured in acetone when compared to the one that is measured in water. 2. Would the reverse reaction of t-butyl alcohol with NaCl be as fast, faster or slower than the reaction studied here? Explain. The reverse reaction of t-butyl alcohol with NaCl be the slower or either not even occur at high possibility, because hydroxide ion is stronger than any halogen and would not be easily displaced by them. This is due to its higher affinity towards one proton whereas the halogens can be stable on its own halide state i.e. Bromine (Br) can exist independently as Br2, Cl as Cl2 and so on but OH needs a proton to attach with and that bond is not easily broken since it is not sharing an electron but fulfilling its own octet by getting one electron.

Appendix: I-A: Variation in hydroxide concentration: Using the following equation (eq.1), k was determined:

For 10%: k = [2.303 * log (1 / (1 10/100))] / 59 = 1.79 * 10-3 For 20%: k = [2.303 * log (1 / (1 20/100))] / 116 = 1.92 * 10-3 For 30%: k = [2.303 * log (1 / (1 30/100))] / 269 = 1.33 * 10-3+ Therefore,
% reaction time k

10 20 30

59 116 269

0.001786 0.001924 0.001326

I-B: Variation of t-Butyl concentration In order to determine the order of reaction, final concentration was needed to be determined using the following relationship (eq. 2):

Cf = CiVi/Vf
[t-Butyl]I (M) 0.2 0.1 0.1 Volumei (ml) 3.0 3.0 3.0 Volumef (ml) 10 10 20

For 0.2M: Cf = 0.2 * 3.0 /10 = 0.06M For 0.1M: Cf = 0.1 * 3.0 /10 = 0.03M For 0.1M: Cf = 0.1 * 3.0 /20 = 0.015M Therefore,
[t-Butyl]I (M) 0.2 0.1 0.1 Volumei (ml) 3.0 3.0 3.0 Volumef [t-Butyl]f (ml) (M) 10 10 20 0.06 0.03 0.015

II Study of temperature variation Value of k was determined using the equation 1, and then the activation energy:
% Temperature Time Average Average K values

reaction 10% 10% 10% 10% 10%

(K) 284 284 294 304 304

(seconds) 458 462 59 16 14

time (seconds)

temperature (K)

460 59 15

284 294 304

0.0002291 0.001786 0.0070567

For 284oK: k = 2.303 * (log (1/(1-10/100))) / 460 = 0.0002291 For 294oK: k = 2.303 * (log (1/(1-10/100))) / 59 = 0.001786 For 304oK: k = 2.303 * (log (1/(1-10/100))) / 15 = 0.0070567 Activation energy determined using ln k vs. 1 / T: Y = mx + b: ln k = (-Ea/R)(1/T) + constant. Since mx = (-Ea/R)(1/T), m = (-Ea/R). Hence, Ea = -m *R Ea = -14814 * (-1) * 8.314 * 103 = 123.16 kJ/mol Error estimate for ln k vs 1/T: Standard error * 100 = 0.2308 * 100 = 23.08%


Regression Statistics Multiple R R Square Adjusted R Square 0.9955 09 0.9910 38 0.9820 77

Standard Error Observati ons

0.2308 02 3

ANOVA df Regressio n Residual Total 1 1 2 SS 5.8909 05 0.0532 69 5.9441 75 MS 5.890 905 0.053 269 F 110.5 871 Signific ance F 0.06035 6

Coeffici ents Intercept 43.873

Standa rd Error 4.7971 97 1408.7 44

t Stat

Pvalue 0.069 334 0.060 356

Lower 95% 17.0812 32714.2

Upper 95% 104.8 272 3085. 382

Lower 95.0% 17.08 12 32714 .2

Upper 95.0% 104.8 272 3085. 382

9.145 549 10.51 6

X Variable 1

14814. 4

Activation energy determined using log k vs 1/T: Y = mx + b; -log k = (Ea/2.3R)(1/T) + constant. Since mx = (Ea/2.3R)(1/T), m = Ea/2.3R. therefore, Ea = m * 2.3R Ea = 6437.9 * 2.3 * 8.314 * 10-3 = 123.11 kJ/mol

Error estimate for log k vs. T: Standard error * 100 = 0.09983 * 100 = 9.983%


Regression Statistics Multiple R R Square Adjusted R Square Standard Error Observati ons 0.9955 51 0.9911 22 0.9822 44 0.0998 26 3

ANOVA df Regressio n Residual Total 1 1 2 SS 1.1125 13 0.0099 65 1.1224 78 MS 1.112 513 0.009 965 F 111.6 395 Signific ance F 0.06007 3

Coeffici ents

Standa rd Error

t Stat


Lower 95%

Upper 95%

Lower 95.0%

Upper 95.0%


19.068 1 6437.9 23

2.0748 77 609.30 81

9.189 99 10.56 596

0.069 002 0.060 073

45.4319 1304.07

7.295 707 14179 .92

45.43 19 1304. 07

7.295 707 14179 .92

X Variable 1