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EXPERIMENT 1

DETERMINATION OF ACTIVITY AND


ACTIVITY COEFFICIENT FROM CELL EMF
OBJECTIVES
At the end of this exercise, the students should be able to determine the activity
and activity coefficient of various HCl solutions from the measured cell emf.
LIST OF CHEMICALS/MATERIALS

Standard 0.010M NaOH

stock 0.025M HCl

pycnometer
beakers (100mL)

LIST OF APPARATUS AND SET-UP

pH meter with mV scale


volumetric flasks (100 mL)

SAFETY PRECAUTIONS
NaOH and HCl are strong base and strong acid, respectively. These chemicals
are corrosive, irritant and permeator to the skin. These are also eye irritant.
Ingestion of these is very hazardous. Vapors of these chemicals are lung sensitizer.
In case of eye and skin contact, immediately flush with running water for at least 15
minutes. If inhaled, move to fresh air. If not breathing, artificial respiration must be
administered. If breathing is difficult, give oxygen. In case of ingestion, do not
induce vomiting unless directed to do so by a medical personnel. Get medical
attention immediately.
DISCUSSION
Consider the following glass calomel electrochemical cell:
Ag,AgCl soln of known pH/ glass/ soln of unknown pH/ KCl(satd),Hg 2Cl2,Hg
The potential of the glass electrode can be expressed as

E E0

2.303RT
RT
pH E 0
ln aH

(1-1)

Since the electrode uses saturated KCl solution, its potential is constant, so equation
(1-1) becomes the equation for the cell emf (although E becomes another constant
E0g). At 25OC this equation becomes

E Eg0 0.0592log aH
(1-2)
CHM156L. Physical Chemistry Laboratory 2

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EXPERIMENT 1: DETERMINATION OF ACTIVITY AND ACTIVITY


COEFFICIENT FROM CELL EMF

For uni-univalent solutions like HCl,

aH a m m
(1-3)
Equation (1-2) then becomes

E Eg0 0.0592log 0.0592log m


(1-4)
For dilute solutions, one can apply the Debye-Huckel Limiting Law

log 0.511 m

(1-5)

to give the equation

E Eg0 0.0296 m 0.0592log m


(1-6)
or,

E 0.0592log m Eg0 0.0296 m


(1-7)

0
g

0
g

can then be determined from experimental values of E and m. Once the value of
is known, the values of and aH+ can be calculated for each value of m.
PROCEDURE
1. a.

Prepare in duplicate 100 mL each of 0.025 M to 0.005 M HCl solutions.

b.

Pour about 60 mL of each of these solutions in 100 mL beakers.

c.

Equilibrate them in a 25oC water bath for 15 minutes.

2. Measure the emf developed in each solution using a pH meter in the mV scale.
3. Measure the density of each of the above solutions using a pycnometer.

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: DETERMINATION OF ACTIVITY AND ACTIVITY


COEFFICIENT FROM CELL EMF

4. Titrate 10 mL of each of the above solutions and measure the concentration in molality with
standard 0.010M NaOH. Make two trials.

ANALYSIS OF DATA

1.

Calculate the density of each mixture using the following equation:

mixture =

mass mixture
x water at T
mass water

bath

2. Using the density of the mixture, calculate the mass of the 10 mL aliquot.
3. Determine the number of moles of HCl present in each mixture using the
titration data.
4. Convert the moles of HCl to mass of HCl using the molar mass of HCl.
5. Determine the actual molality of HCl mixture using the following equation:

actual molality =

6. Determine

o
g

mol HCl
( mass aliquotmass of HCl ) Kg

by linear regression using the following:

E 0.0592log m Eg0 0.0296 m


7. Calculate the values of using equation (1-4) and aH+ using equation (1-3)
from each value of m.

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: DETERMINATION OF ACTIVITY AND ACTIVITY


COEFFICIENT FROM CELL EMF

CHM 156L
Section:
Professor:
Group No:
Members :

_____________________
Date Performed: _____________________
_____________________
Date Submitted: _____________________
_____________________
____________________________
____________________________
____________________________
____________________________
____________________________
____________________________

REPORT SHEET
EXPERIMENT 1
DETERMINATION OF ACTIVITY AND ACTIVITY COEFFICIENT FROM CELL EMF
Table 1.1. Density measurements of the HCl solutions.

Molarity
0.005
0.010
0.015
0.020
0.025
H2O

Replicat
e

Mass of pycnometer, g
empty

+ mixture

Mass of
mixture,
g

Ave ,

g/mL

g/mL

I
II
I
II
I
II
I
II
I
II
I
II

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: DETERMINATION OF ACTIVITY AND ACTIVITY


COEFFICIENT FROM CELL EMF

Table 1.2. Titration of the HCl solutions with standard 0.01M NaOH.
Parameter
Vol. aliquot,
mL
Mass

0.005
I
II
10.0 10.0
0

Nominal molality of HCl solutions, m


0.010
0.015
0.020
0.025
I
II
I
II
I
II
I
II
10.0 10.0 10.0 10.0 10.0 10.0 10.0 10.0

aliquot, g
Vol NaoH
Final rdg, mL
Initial rdg,
mL
Vol used, mL
Mol HCl
In aliquot
Mass HCl, g
Actual
molality
Table 1.3. Measured emf and other calculated data for the HCl solutions.
Actual
molality
I
II

emf, volts
I

II

II

aH+
II

II

Signature: ______________
Date completed: ______________
POST LAB QUESTIONS
1. How does a glass calomel electrode works?

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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EXPERIMENT 1: DETERMINATION OF ACTIVITY AND ACTIVITY


COEFFICIENT FROM CELL EMF

2. What are the implications of the values of the activity and activity coefficients
on the behavior of the different mixtures?
3. What are the possible sources of errors? Explain the effect of these errors on
the results.

CHM 156L Physical Chemistry for Engineers 2 (Laboratory)

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