Phenolphthalein-NaOH Kinetics

The objective of the current experiment was to measure the rate of reaction of the pick
phenolphthalein
2- 2-
(p ) with an excess amount of sodium hydroxide. The concentration of (P ) is being determined with
the color shade of the solution. Phenolphthalein is well known common indicators used to determine
the end point in acid-base titrations. As the concentration of base increases in the solution the
phenolphthalein fades its color with gentle stirring. However, the fading of phenolphthalein in basic
solution is an excellent example of second order reaction kinetics.

Phenolphthalein (C20H14O4) has a complex structure in colorless form the structure is not important to
this experiment. When the pH Increase to 8 or lower, the phenolphthalein could be shown using an
empirical formula of H2P. While for the range of pH range of 8-10 both acidic protons are quickly
expelled from H2P by NaOH, (OH - ). to give the pink P 2-particle as indicated by the condition. At a pH
2- -
above 10 the pink color slowly fades as P reacts further with NaOH, (OH ), to give the colorless
3-
POH ion according to the equation:
P2- + OH- = POH3-
pink colorless

The rate law for this second order reaction can be expressed
as:
2- m n 2- m n
Rate = k2 [P ] [NaOH] or Rate = k2[P ] [NaOH]

The target of this examination is to show that both m and n are equivalent to one or that the response
is first order in phenolphthalein and first order in NaOH (OH-particle). In this experiment the solution
will be strongly basic with just a few drops of phenolphthalein. In any of the individual runs, the NaOH
3 4
focus surpasses that of phenolphthalein by a factor of 10 to 10 . Hence for each trail NaOH
concentration remains constant while the rate constant is shown as follow:
-2 m
Rate = k1[P ]
In this new rate law
n
k1 = k2[NaOH]
2-
the above reaction is also called “pseudo lst order” in phenolphthalein, the species P , if m = 1. If the
2-
reaction is indeed first order in phenolphthalein (m = 1) then a plot of ln[P ] versus time will give a
straight line with a slope equal to –k1.

In this experiment, the volume of P2 in the reaction solution is determined by measuring the
absorbance of 550 nm of light. If Io is the intensity of the light entering the solution at 550 nm and I is
the intensity of the light leaving the solution, then the transmittance, T, of the solution is given as I /
Io. Transmittance is also expressed as a percentage (I / Io) x (100%). The absorbance, A, rather than
the transmittance, is often used to absorb the amount of light the solution absorbs. Absorbance is
defined by equations A = -log(T) or A = log(lo / I). The absorbance of the solution depends on the
amount of light absorbing species in the solution and the length of the solution through which the
light passes. This relationship is known as Beer's Law and is mathematically expressed as A = abc. Here
is the proportionality constant (molar absorption when the concentration units are molar); b is the
length of the path of radiation through the solution and c is the concentration of the solution. As a
1
consequence, [P2-] is explicitly proportional to the absorbance A of the solution at 550 nm. Thus, a
2-
plot of ln(A) versus time will give a straight line if the reaction is first order in P and its slope will be
-k1. The rate law is then:
m n
Rate = k2 (Absorbance) [NaOH]

By measuring the reaction rate at several different concentrations of NaOH, it can be shown that the
reaction is first order in NaOH and the rate constant, k2 can be evaluated.
k n
= k2[NaOH]
1
if n = 0, then k2 will equal k1 for all four runs.
If n = 1 then k2 equals k1 divided by [NaOH] and k1/[NaOH] will be constant for all four runs.
2 2
If n = 2 then k2 equals k1 divided by [NaOH] and k1/[NaOH] will be constant for all for runs. Thus,
the reaction order in NaOH can be determined.

EXPERIMENTAL PROCEDURE

Preparation of Standard Solutions

1. Some measurements in this experiment were not particularly critical; other measurements
might be determined accurately.
2. The exact concentration of the initial phenolphthalein solution and the exact time of mixing
were not critical. The thi ng important, was knowing the concentration of the initial NaOH
solution, making dilute NaOH solutions very accurately, measuring the time intervals between
absorbance readings accurately, and keeping the total ion concentration (the ionic strength) of
all the runs constant.
3. The last factor was important because the reaction rate depends on the ionic strength of
the solution since the reaction involves the approach of two negatively charged ions and their
mutual repulsion was decreased in an environment containing inert (spectator) ions.
4. A constant ionic strength was maintained in the solutions by substituting 0.300 M NaCl for
0.300M NaOH.
5. Diluted one mL of a phenolphthalein solution with 4 mL of ethyl alcohol.
6. Weighed 1.200 grams of concentrated NaOH solution (50% NaOH by mass) solution into a
50 mL beaker and transfer it to a 50 mL volumetric flask. Rinsed the beaker several times with
distilled water and pour that solution into the volumetric flask. Diluted to the mark with
distilled water.
7. Weighed out 0.878 grams of NaCl in a 50 mL volumetric flask. Added a small amount of
distilled water, swirl to dissolve the salt and then diluted to the mark with distilled water.
8. Set the wavelength knob to 550 nm. With no cuvette in the cell compartment, used the left
dial to set the meter to zero % transmittance. Filled a clean cuvette with distilled water and
place in the cell compartment. Adjust the % transmittance to read 100% using the right dial.
Do not touch the wavelength, zero percent and 100% dials once the instrument is calibrated.

2
 Kinetic Runs
Run No. 1:
Fill a cuvette to the B & L mark with 0.300 M NaOH, add one drop of phenolphthalein solution, and
invert to mix the solutions. Place the cuvette in the Spintronic 20. Readings of absorbance vs time
should begin when the absorbance value reaches 0.60. If the initial absorbance is over 0.60 leave the
cuvette in the Spintronic 20 and wait until the reading drops to 0.60. If the initial absorbance is
below
0.60 remove the cuvette, add another drop of phenolphthalein solution and invert to mix. Reinsert
the cuvette and wait until the absorbance drops to 0.60. Start your timing when the absorbance is
0.60. Zero time is when you take your initial absorbance reading. Record the absorbance every 0.50
minutes after your initial reading for a total of 3.0 minutes.

Run No. 2: Prepare 0.200M NaOH by pipetting 20 mL of 0.300 M NaOH solution into a small beaker
and pipetting 10 mL of 0.300 M NaCl into it. Fill a cuvette to the B & L mark with the resulting 0.200
M NaOH solution, add one drop of phenolphthalein solution and invert to mix. Place the cuvette in
the Spectronic 20 and start your measurements when the absorbance is 0.60. Take readings every
1.0 minutes for a total of 6.0 minutes.

Run No. 3: Prepare 0.100M NaOH by pipetting 10 mL of 0.200 M NaOH into a small beaker and
pipetting 10 mL of 0.300 M NaCl into it. Fill a cuvette to the B & L mark with the 0.100 M NaOH
solution, add one drop of phenolphthalein solution, and invert to mix. Place the cuvette in the
Spectronic 20 and start absorbance readings when the initial value reaches 0.60. Take subsequent
absorbance readings every 2.0 minutes for a total of 12 minutes.
Name: Partner:

Run #1 Run #2

0.300 M NaOH 0.200 M NaOH

Time (min) Absorbance (A) ln(A) Time(min) Absorbance (A) ln(A)
0 0.611 -0.49265832 0 0.223 -1.500583508

10 0.572 -0.558616288 10 0.216 -1.532476871

20 0.536 -0.623621118 20 0.21 -1.560647748

30 0.5 -0.693147181 30 0.203 -1.5945493

40 0.468 -0.759286983 40 0.197 -1.62455155

50 0.44 -0.820980552 50 0.191 -1.655481851

60 0.414 -0.881889305 60 0.185 -1.687399454

70 0.39 -0.94160854 70 0.18 -1.714798428

 80 0.368 -0.999672341 80 0.175 -1.742969305

90 0.348 -1.055552799 90 0.17 -1.771956842

100 0.329 -1.111697528 100 0.165 -1.801809805

110 0.311 -1.167962367 110 0.161 -1.826350914

120 0.295 -1.220779923 120 0.157 -1.851509474

130 0.28 -1.272965676 130 0.155 -1.864330162

140 0.265 -1.328025453 140 0.153 -1.877317358

150 0.252 -1.378326191 150 0.149 -1.903808973

160 0.239 -1.431291727 160 0.146 -1.924148657

170 0.227 -1.482805262 170 0.144 -1.937941979

180 0.216 -1.532476871 180 0.141 -1.958995389

190 0.206 -1.57987911 190 0.137 -1.987774353

Run #3

0.100 M NaOH
Time (min) Absorbance (A) ln(A)
0 0.725 -0.321583624

10 0.749 -0.289016295

20 0.739 -0.302457358

30 0.727 -0.318828801

40 0.706 -0.348140041

50 0.677 -0.390084006

60 0.661 -0.414001439

70 0.653 -0.42617815

80 0.651 -0.429245637
90 0.649 -0.432322562

100 0.645 -0.438504962

110 0.639 -0.447850825

120 0.633 -0.457284857

130 0.625 -0.470003629

140 0.614 -0.487760351

150 0.604 -0.504181081

160 0.596 -0.517514612

170 0.594 -0.52087596

180 0.598 -0.514164525

190 0.598 -0.514164525

Name: Partner:
Calculations and Results

Order of Reaction in Phenolphthalein

All four curves plotted on one graph and the slopes determined using the statistics portion of the
program.

Plot graphs of ln(A) vs. time (0-190 minute range for the x-axis) for each of the four runs. Evaluate
the rate constant, k1, for each run from the slope of each curve. k1 = -(slope)
0
0 20 40 60 80 100 120 140 160 180 200

-0.5 f(x) = − 0 x − 0.31

f(x) = − 0.01 x − 0.53

-1

-1.5
f(x) = − 0 x − 1.53

-2

-2.5

ln(0.3 M NaOH)
Linear (ln(0.3 M NaOH)) ln(0.2 M NaOH)
Linear (ln(0.2 M NaOH)) ln(0.1 M NaOH)
Linear (ln(0.1 M NaOH))

-2
Question: Are all the runs first order in P (Absorbance)? Explain your answer.
Answer: All three curves of ln(Absorbance) vs. time will be linear which means overall reaction is
first order in phenolphthalein

Evaluation of k1 for each run (k1 = -slope).

Run No. [NaOH] (M) k1

1 0.3 0.0057

2 0.2 0.0025

3 0.1 0.0012
 Order of Reaction in NaOH and Evaluation of k2
n
The rate constant, k2 equals k1 /[NaOH] where n equals 0, 1, or 2. Evaluate the rate constant, k2,
for runs 1 through 4 as indicated for columns A, B, and C in the table below.

st nd
A (Zero order in base) B (1 order in base) C (2 order in base)
- 0 - - 2
Run [NaOH] k1 k2 = k1/[NaOH ] k2 = k1/[NaOH ] k2 = k1/[NaOH ]
No. (M) or k2 = k1
1 0.3 0.0057 0.0057 0.019 0.063

2 0.2 0.0025 0.0025 0.0125 0.0625

3 0.1 0.0012 0.0012 0.012 0.12

Question: In which column A, B, or C is the calculated value of k2 constant for all three runs ?

Answer: The column B has the calculated values for k2

Question: Is the reaction zero, first, or second order in NaOH? Why

Answer: The Reaction is first order. When the amount of water is relatively large, the reaction goes
practically to completion (the equilibrium shifts to the right) and the rate is first order with respect to the
ester. The hydrolysis takes place slowly with pure water and is catalyzed by acids. where k1 is the first
order rate constant.