SIC1012

LAB REPORT EXPERIMENT 6: DETERMINATION OF RATE

CONSTANT OF A DISSOCIATIVE REACTION

PREPARED FOR: DR VANNAJAN S. LEE

NAME SUMAYYAH BINTI LOKMAN

MATRIX NO. 22003285/1

SEMESTER 1

OCCURANCE 9

DATE OF 15th MAY 2023

EXPERIMENT
OBJECTIVE: To determine the rate constant of a dissociative reaction of 4-Methyl-4-
hydroxy-2-pentanone, MHP (diacetone alcohol)

INTRODCUTION
4-Methyl-4-hydroxy-2-pentanone, MHP (diacetone alcohol) undergo dissociation process in
the presence of hydroxyl ion to form acetone.

Figure 1: Reaction mechanism for dissociation reaction of 4-Methyl-4-hydroxy-2-pentanone,

MHP (diacetone alcohol)

Step A shows the overall reaction for dissociation of 4-Methyl-4-hydroxy-2-pentanone, MHP

(diacetone alcohol) while (B), (C) and (D) shows the steps of the reaction in order. Step (C)
and (D) are the slowest step which is also known as the rate determining steps.
Rate constant, k is given by:
𝑑[𝑀𝐻𝑃]
− = 𝑘[𝑀𝐻𝑃]
𝑑𝑡
𝐾3 𝐾1 [𝑂𝐻 − ]
𝑘=
𝐾2 [𝐻2 𝑂]
this equation can be rewrite as:

[𝑀𝐻𝑃]0 𝑎
𝑙𝑛 = 𝑘𝑡 OR 𝑙𝑛 = 𝑘𝑡
[𝑀𝐻𝑃] (𝑎−𝑥)

the previous equation can be represented as:

(𝑉 − 𝑉∞ )
= 𝑒 −𝑘𝑡
(𝑉0 − 𝑉∞ )

MATERIALS
Apparatus: dilatometer, conical flask, burette, pipette, thermometer, stopwatch
Chemicals: 0.1 mol dm-3 Sodium hydroxide, MHP (diacetone alcohol), acetone.

EXPERIMENTAL PROCEDURE
TEST 1
1. The dilatometer is placed in a 30℃-water bath with only the bulb immersed in the
water.
2. 34 cm3 of 0.1 mol dm-3 sodium hydroxide (NaOH) is added into a conical flask using a
burette. The flask is then stoppered and placed in the same water bath.
3. 1 cm3 of acetone is added to the conical flask (in step 2) after 15 minutes through a
pipette, followed by 2 cm3 of MHP from different pipette. The contents are then poured
into the funnel of dilatometer after swirled. The stopcock is opened and the solution is
allowed to fill up the bulb until exactly below the capillary.
4. The position of the meniscus is recorded every 30 seconds for 600 seconds with the
stopcock closed.
5. A similar set of reading is taken (i.e., ∆t=600s) after allowing it to remain for another
600 seconds.

TEST 2
The above procedure is repeated using 35 cm3 of NaOH solution and 2 cm3 of MHP only
(without acetone)
RESULTS
TEST 1

Time, t /s V V’ V’-V ln (V’-V)

30 2.10 11.60 9.50 2.2513

60 2.60 11.70 9.10 2.2083

90 3.00 11.80 8.80 2.1748

120 3.30 11.90 8.60 2.1518

150 3.70 12.10 8.40 2.1282

180 4.10 12.15 8.05 2.0857

210 4.50 12.20 7.70 2.0412

240 4.80 12.30 7.50 2.0149

270 5.10 12.40 7.30 1.9879

300 5.50 12.50 7.00 1.9459

330 5.80 12.60 6.80 1.9169

360 6.10 12.70 6.60 1.8871

390 6.40 12.75 6.35 1.8485

420 6.70 12.80 6.10 1.8083

450 7.00 12.90 5.90 1.7750

480 7.30 13.00 5.70 1.7405

510 7.50 13.10 5.60 1.7228

540 7.80 13.15 5.35 1.6771

570 8.00 13.20 5.20 1.6487

600 8.20 13.25 5.05 1.6194

 ln (V’-V) against t
2.5

1.5
ln (V’-V)

1
y = -0.0011x + 2.2824

0.5

0
0 100 200 300 400 500 600 700
Time, t /s

Figure 2: Graph of ln (V’-V) against t for the reaction with acetone

TEST 2

Time, t /s V V’ V’-V ln (V’-V)

30 0.70 12.30 11.60 2.4510

60 1.40 12.40 11.00 2.3979

90 2.70 12.60 9.90 2.2925

120 3.20 12.70 9.50 2.2513

150 3.70 12.80 9.10 2.2083

180 4.10 12.90 8.80 2.1748

210 4.50 13.00 8.50 2.1401

240 4.90 13.10 8.20 2.1041

270 5.30 13.20 7.90 2.0669

300 5.60 13.30 7.70 2.0412

330 6.00 13.40 7.40 2.0015

360 6.40 13.50 7.10 1.9601

390 6.70 13.60 6.90 1.9315

 420 7.00 13.70 6.70 1.9021

450 7.30 13.75 6.45 1.8641

480 7.60 13.80 6.20 1.8245

510 7.90 13.90 6.00 1.7918

540 8.10 14.00 5.90 1.7750

570 8.40 14.10 5.7 1.7405

600 8.70 14.15 5.45 1.6956

ln (V’-V) against t
3

2.5

2
ln (V’-V)

1.5

1
y = -0.0012x + 2.4189
0.5

0
0 100 200 300 400 500 600 700
Time, t /s

Figure 3: Graph of ln (V’-V) against t for the reaction without acetone

GRAPH ANALYSIS
TEST 1(with acetone)

Graph of ln (V’-V) against time, t will give a slope of -k:

𝑙𝑛(𝑉′ − 𝑉) = −𝑘𝑡 + 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

By comparing this equation to y=mx+c,

𝑚 = −𝑘
Based on this graph,
y = -0.0011x + 2.2824 where m = -0.0011
-k= - 0.0011,
k = 0.0011
k= 1.1 × 10−3 𝑠 −1
TEST 2 (without acetone)

y = -0.0012x + 2.4189 where m = -0.0012

-k= - 0.0012,
k= 0.0012
k= 1.2 × 10−3 𝑠 −1

DISCUSSION
Based on the graph from test 1 and test 2, the rate constant of reaction without acetone is higher
compared to reaction with acetone. This means that the reaction without acetone is faster
compared to the reaction with acetone. The dissociation of MHP will give acetone as the
product. Therefore, when acetone is added in test 2, the concentration of the product will
increase and the equilibrium will shift to the left to decrease the concentration of the product.
This situation favoured the reverse direction and some of the acetone will be converted back
into MHP. As a result, the concentration of MHP will increase and the rate of reaction with
acetone become less compared to the reaction without acetone. The decomposition rate of MHP
is inversely related to concentration of acetone. This is shown by equation:
𝑑[𝑀𝐻𝑃] K 5 K 3 K1 [MHP][OH - ]
=( )( )
dt K4K2 CH3 COCH3
PRECAUTION STEPS
1. Make sure the temperature is kept constant throughout the whole experiment because
temperature will affect the rate constant.
2. Make sure the meniscus level aligns with the solution in the capillary to avoid parallax
error.
3. Dry the dilatometer thoroughly to avoid formation of air bubbles in the capillary that
will affect the reading.
4. Wash the burette and pipette with distilled water and followed by the solution that will
be used later in that apparatus.

CONCLUSION
In conclusion, the rate constant of the reaction with acetone and reaction without acetone are
1.1 × 10−3 𝑠 −1 and 1.2 × 10−3 𝑠 −1 respectively. The presence of acetone give a slight effect
on the rate constant as it increase the concentration of product and reverse direction is favoured.

REFERENCE

18.8: Rate Law and Specific Rate Constant. (2016, June 27). Chemistry LibreTexts.

https://chem.libretexts.org/Bookshelves/Introductory_Chemistry/Introductory_Chemi

stry_(CK-12)/18%3A_Kinetics/18.08%3A_Rate_Law_and_Specific_Rate_Constant

Effect of Concentration on Equilibrium | Chemical Equilibrium. (2018, February 14). Nigerian

Scholars. https://nigerianscholars.com/tutorials/chemical-equilibrium/effect-of-

concentration-on-equilibrium/

ketua_kimia@um.edu.my. (n.d.). University of Malaya. Retrieved from Laboratory Manual:

https://kimia.um.edu.my/LabManual/fizikal/expt-3-manual.pdf