KING FAHD UNIVERSITY OF PETROLEUM AND

MINERALS
2021
COLLEGE OF SCIENCES
CHEMISTRY DEPARTMENT

CHEM 311
Experiments in Physical Chemistry
 CONTENTS
S.NO NAME OF THE EXPERIMENT PAGE NO

1 FORMAT TO WRITE LAB REPORT 05

ERROR ANALYSIS, REJECTION RULE, AND HOMEWORK

2 07
PROBLEMS

3 MEASUREMENT OF DENSITY 15

4 CONDUCTIVITY OF STRONG & WEAK ELECTROLYTES 21

TRANSFERENCE OF IONS/
5 25
MOVING BOUNDARY METHOD

6 ELECTROCHEMISTRY (E.M.F.) 31

7 DETERMINATION OF DIFFUSION POTENTIAL 37

8 KINETICS OF ETHYL ACETATE WITH HYDROXIDE ION 43

9 KINETICS USING SPECTROSCOPY 47

10 KINETICS OF CANE SUGAR INVERSION 53

11 ADSORPTION ISOTHERMS OF ACETIC ACID 59

12 SURFACE TENSION BY RING METHOD 63

13 LIQUID VISCOSITY 67

14 GAS VISCOSITY 73

15 ABSORPTION SPECTRUM OF CONJUGATED DYE 77

16 FLUORESCENCE QUENCHING OF RHODAMINE B DYE 83

17 VIBRATIONAL-ROTATIONAL SPECTRA OF HCL AND DCL 90

 5

FORMAT FOR LABORATORY REPORTS

Laboratory reports should be prepared in a style roughly comparable to that of a

research paper. They should be typed or neatly handwritten using one side of the page
only. Accuracy of data and calculations, and the discussion, will account for most of
the grades, but neatness and clarity of presentation are important and will also be
considered. The following guidelines could be used during preparation of the
laboratory report.

Title Page: (A single page that contains)

Laboratory Number, Title of experiment, Student Name and Student Number, Name
of Partner(s) if any, Date Performed, Date Submitted etc. should be given.

Report Pages:

In the coming pages, student should use his own words, not
copied from lab handout, to fulfil the following sections.

Introduction:

1. A brief statement of the purpose of the experiment.

2. A very brief outline of necessary theory together with important equations.

Experimental Procedure:

1. A brief description on any changes in the given procedure need to be

presented.

2. All the used materials and equipment should be listed here.

3. Make reference and citation to the pertinent text or handout used for this
work,

Data:

1. Present raw data in table form wherever possible. All tables should have titles,
and units should be given in the column headings.

2. Record the uncertainties in each type of measured value.

6 Format to Write Lab Report

3. List all the literature values “True Values” and their citation(s).

Calculations:

1. Give one sample each type of calculations used in obtaining the results.

2. Use the correct number of significant figures in all calculations.

3. In determining slopes and intercepts, use a linear regression program rather

than a graphical method.

4. Write down the equation obtained, together with the correlation coefficient
value.

5. Describe the calculation of uncertainties in derived results.

Discussion:

1. Summarize the results by giving the most important numbers obtained,

together with their uncertainties, to the correct number of significant figures.

2. Use the rejection rule to test the outlier points or experimental observations as
needed.

3. Compare the results to literature values wherever possible and identify the
value of error percent in the measured or estimated observations.

4. Discuss sources of error and how they could be avoided.

5. Discuss the physical or chemical significance of the results. Answer any

question.

Reference:
List all references cited in the report in the proper IUPAC format.

More detailed advice on the preparation of lab reports can be

found on pages 12 to 28 of the lab Textbook [1].

[1] Experiment in Physical Chemistry, 5th ed. Shoemaker, Garland, Steinfeld &
Nibler, McGraw Hill, 1988, pp 12-28.
 7

ERROR ANALYSIS AND REJECTION RULE

I. Introduction
In colloquial English, an Error means a mistake or blunder, i.e., 2+2=5 is an error.
However, when we refer to errors in our experimental results, we mean something
quite different. In principle we can find all of our mistakes and correct them. Yet even
with everything done perfectly, any measurement of a macroscopic continuous
property is inherently approximate. It is impossible, even in theory, to measure
exactly a temperature, or mass, or length, etc.

We define the error in a measurement as

Error = Ei = observed value - true value

A dilemma from this definition is that we seldom know the true value; if we did, we
would use it and have zero error. It is very important to know the approximate sizes of
the errors in our results. One way that we study the sizes of errors is to repeat the
same measurement many times. Finally, you can represent the average of the
observations using the following notation:
X 
where
n
1
X = average value =
n
x
i 1
i

n = number of measurements

x i = value measured in ith experiment

1
1 n 2
 = standard deviation =   i2 
 n i 1 

I = deviation in x i = x i - X
For small sample, the standard deviation can be rewritten as follows

1/2
 n 2 1 n  
2

 x i   x i  
 n  i 1  
   i 1 
 n 1 
Then you can determine the error percent for any observation using

% error in x i =  ei  x 100
8 Measurement of Density

where
Ei xi  x
ei = relative error in x i = 
x x
x = exact, calculated, or literature value.

II. Rejection of discordant:

One of the most difficult decisions which faces research workers is the rejection of
data, which they suspect may be wrong. Sometimes, a data set of replicated
determinations contains one result that is distinctly different from the other points (an
outlier). When are we justified in discarding such a point? When a known error
occurs, such as spillage or use of an incorrect reagent, we discard the result regardless
of its value. But in case of unknown source of the error a method called “Rejection
Rule” should be applied. Any of the following methods can be used to test the
discordant values, which are based on the normal probability distribution curve as
shown below.

A) Method 1:

By evaluating the area under the normal probability distribution curve in Figure 1,
when n, the number of measurements, is plotted against the experimental distribution
of deviations from the average x , shows different probabilities.

RANGE PROBABILITY
x   0.684
x  2 0.954
x  3 0.997

Figure 1: The normal probability distribution curve and the possible probabilities
at the different ranges of errors

It is noticed that there is a 95.4 % chance that a result will be in the range x  2, i.e.
a less than 5% chance of being outside this range. Therefore, it is possible to "reject"
data having standard deviation of 3 and above and now by calculatingx and 
without using xk and test the following
 Measurement of Density 9

If the result is larger than 2, xk is rejected ………… (1)

EXAMPLE: Suppose five tests of a liquid density at room temperature give

Trail density (g/cm3)

1 0.8524
2 0.8531
3 0.8576
4 0.8535
5 0.8519

Observation: Compared to the others, trial # 3 appears to be different.

Question: Can student discard result # 3, and just use the other four values?
Answer: Omitting trial # 3 value and find the average and the standard deviation of
the other points as follows
 = 0.8527 g/cm3, and  = 0.0007 g/cm3
Using equation (1) gives (0.8576 - 0.8527)/0.0007 = 7.0, thus the value is greater than
2, so we would reject the value 0.8576.

B) Method 2:

Other simpler data rejection method is called the "4D rule" that is applicable to small
data sets with at least four determinations, where a chance that a result is 99.7%
within the normal distribution, i.e. it is in the range of X ± 3 is only included in the
calculated average. In this method student should follow the following steps:

1. Calculate the mean of the points (excluding the questionable point).

2. Calculate the deviation from the mean of each data point (including the
questionable one).
3. Determine the mean of the deviations of all of the samples (excluding the
questionable one).
4. If the deviation of the questionable point is equal to or greater than four times
the obtained value in step 3, “mean of the deviation,” that point may be
rejected.

EXAMPLE. Analysis of aspirin content of tablets by titration with base gives

Run # mL of Base
1 37.27 mL
2 37.24 mL
3 37.29 mL
4 37.18 mL
10 Measurement of Density

Observation: Compared to the others, run # 4 appears to be different.

Question: should run # 4 be discard?

Answer: following 4D-rejection rule as follows to make the correct decision

- Step 1: Mean of the three agreeing values
(37.27 + 37.24 + 37.29)/3 = 37.27
- Step 2: Deviation of each point from the mean
1) |37.27 - 37.27| = 0.00
2) |37.24 - 37.27| = 0.03
3) |37.29 - 37.27| = 0.02
4) |37.18 - 37.27| = 0.09
- Step 3: Mean deviation of the three agreeing values
(0.00 + 0.03 + 0.02) / 3 = 0.017 (For an intermediate calculation, an extra
decimal is kept)
- Step 4: Compare the deviation of the questionable point step 3-mean
0.09/0.017 = 5.3, this value is greater than 3, so the questionable point may
be rejected.

III. Uncertainty in the mean value:

The simplest way to indicate the approximate precision of results is to use significant
digits (SD). For example, if you report that the density is 0.8527 g/cm3, we assume
that the final digit is uncertain. A better way of reporting the result is to explicitly
indicate the uncertainty, for example, (0.8527  0.0007) g/cm3, where the uncertainty
is one standard deviation.

Usually experiments require combining the data from several measurements to

calculate a final result. Each individual measurement contains an error, and these
errors are combined together in the calculation. By luck, the errors may cancel each
other, making the result very accurate. Or they may combine to give the maximum
possible error. Usually the error will be somewhere between these extremes. To have
the appropriate SD of the uncertainty in the final answers one of the following method
could be adopted:

A) Interval Method:

The "minimum-maximum" or interval method is an easy way to estimate the error in a

result if the calculation is simple. This method is illustrated in the following example

EXAMPLE. To estimate the error in the calculated density using the following
equation

x = ( mx / mw ) w
 Measurement of Density 11

where
mx = ( 8.2593  0.0021 ) g;
mw = ( 10.0015  0.0009 ) g
w = ( 0.997044  0.000002 ) g/cm3
The maximum x when mx and w are largest, and mw smallest. Thus,
(8.2593  0.0021)
( )  (0.997044  0.000002)  0.823650 g/cm3
x max (10.0015  0.0009)
Similarly
(8.2593  0.0021)
( )  (0.997044  0.000002)  0.823080 g/cm3
x min (10.0015  0.0009)
Averaging these gives  = 0.823365 g/cm3.
Also, we find (0.823650 - 0.823365) = 0.000285.
We round-off and report our result as

x = (0.8234  0.0003) g/cm3

A defect of this approach is that our estimate 0.0003 is not the standard deviation for
x, assuming that the starting error estimates all represented one standard deviation.

B) Propagation of error:
This method of uncertainty determination is more complex by using one or both of the
following mathematical relation(s) of a calculated physical property F as a function of
several measured values x,y,z,..., i.e. F = f (x,y,z,....). The uncertainty of the measured
values are (x), (y), (z) in x,y,z... respectively, can be used at the following basic
equation to estimate the propagated error
F 2 2 F F
2( F)  ( )  ( X)  ( ) 2 2( Y)  ( ) 2 2( Z)
x y z
1) Addition and subtraction only
F = aX  bY  cZ

2( F)  a 2 2( X)  b 2 2(Y)  c2 2( Z)

2) Multiplication and/or division only
F = m (X)a (Y)b (Z)c
2( F) a 2 2 b c
2
( )  ( X )  ( ) 2 2( Y )  ( ) 2 2( Z )
F X Y Z
EXAMPLE. To find density of a liquid, m/V, from the following data

mass of container (mb) = 19.9314  0.0005 g

mass of container + liquid (m(l+ b)) = 28.1038  0.0005 g
volume of liquid (V) = 10.00  0.03 ml
12 Measurement of Density

Mass of liquid: ml = m(l+ b) - mb = 28.1038 - 19.9314 = 8.1724 g, here,

F = X – Y,
therefore, the propagated error in mass is given by
2(F) = 2(x) + 2(y) = 2(.0005)2
(F) = 2(0.0005) = 0.0007 g
m = 8.1724  0.0007 g
Density of Liquid:
m 81724
.
d   0.81724 g / ml
V 10.00
x
here, F
y
Therefore
2( F) 2( x ) 2( y )
 
F2 x2 y2
0.0007 2 0.03 2 1/ 2
( F )  (0.81724)[ ( ) ( ) ]
8.1724 10.00
(F) = (0.81724)7.337x10 -9+9.0 x10-61/2 = 2.45x10-3 g/ml
Then
Density = 0.817  0.002 g/ml

EXAMPLE. Another example on viscosity by Poiseuille's equation:

PR 4 t

8lV
P = 0.010  0.005 atm (pressure)
R = 0.052  0.001 cm (radius)
t = 100.00  0.15 sec (time)
l = 10.10  0.01 cm (distance)
V = 5.856  0.001 cm3 (volume)
The calculated viscosity value is given by
(3.141) (0.01) (0.052) 2 (100)
  4.855 x 108 atm sec  4.918 x 10 2 Poise
8 (10.1) (5.856)

The uncertainty in the viscosity is of the form F = m (X)a (Y)b (Z)c then,
 (P ) 2 4  (t ) 2  (l ) 2  (v ) 2 1/ 2
 ( )   [( )  ( )2  2 (R )  ( ) ( ) ( ) ]
P R t i v

() = [0.25+5.9 x10-3+2.25x10-6+9.8x10-7+ 2.9x10-8]1/2

() =  (4.855 x 10-8) (0.2559)1/2 = 2.45 x 10-8
The final viscosity and uncertainty should be reported in the following format

Viscosity =  = (5  2) x 10-8 atm sec

 Measurement of Density 13

IV. Graphing and Linear Regression in Excel

Regression lines can be used as a way of visually depicting the relationship between
the independent (x) and dependent (y) variables in the graph. A straight line depicts a
linear trend in the data, i.e. the equation describing the line is of first order. For
example, y = 3x + 4. In addition to visually depicting the trend in the data with a
regression line, you can also calculate the equation of the regression line. How well
this equation describes the data (the 'fit'), is expressed as a correlation coefficient, R 2
(R-squared). The closer R2 is to 1.00, the better the fit. After inserting the x and y
data, they should be displayed in a graph as follows:

A) Creating an initial scatter plot

A graph can be produced from a model data in a form of scatter plot. This module will
start with the scatter plot created by using Insert > Chart as shown below,
14 Measurement of Density

Creating a Linear Regression Line (Trendline)

When the chart window is highlighted, you can add a regression line to the chart by
click on + of choosing Chart > Add trendline... From a dialogue box appears, select
the Linear Trend/Regression type, choose the Options tab and select Display
equation on chart, also check the Display r-squared value on chart box, then click
OK to close the dialogue. The chart now displays the regression line as shown below,

Note:
1- the value of R-squared on the graph. The closer to 1.0, the better the fit of the
regression line. That is, the closer the line passes through all of the points.
2- If R-squared value is much less than
1, e.g. 0.873, as in Figure, we would
need to take into account
information such as the number of
data points collected to make an
accurate statistical prediction as to
how well the regression line
represents the true relationship. One
of the action could be taken is to
discard trial # 4. This would improve plot too much to represent a better linear
relationship of x-y plot.
 15

MEASUREMENT OF DENSITY

Objectives:

1. To practice the different methods of the rejection rules.

2. To determine the accurate value of water density at 25 oC.

Introduction:
Density is a measure of the “compactness” of matter within a substance and is defined
by the equation:

Density = mass/volume (1)

The standard metric units in use for mass and volume respectively are grams/milliters
or cubic centimeters. Thus, density has the unit grams/milliter (g/ml) or grams/cubic
centimeters (g/cc). The literature values are usually given in this unit. Density may
be calculated from separate mass and volume measurements. Volume measurements
for liquids or gases are made using a graduated container, e.g., a graduated cylinder,
or a pre-calibrated volume flask. For solids, the volume can be obtained either from
the measurement of the dimensions of solid or by displacement.

In the following experiment, the density of distilled water will be obtained by

measuring the mass and volume separately of a sample of this water using a density
bottle (see photo).

This measurement will be repeated 5 times and the rejection rule may be applied for
any odd result and then the average value should be compared to literature (reference)
values using the following reference equation:
16 Error Analysis & Home Work

Water Density (g/mL) = -0.0004 Temperature (oC) + 1.0064

Procedure:
1. Weigh a clear and dry 50 ml density bottle with its cover on.

2. Fill the bottle to the edge with distilled water without bothering to measuring out

the liquid accurately and then cover it.

3. Carefully place it in a water bath wait 10 to 15 min to reach thermal equilibrium

of the water bath temperature, then remove the bottle from the bath, wipe out any

outside water, and leave it on the working bench for about 5 min to drop down to

the room temperature.

4. Weigh the bottle and distilled water.

5. Refill the bottle with more water (if needed) and repeat step 2 for another four

times.

6. Obtain the water mass in the 5 trials and check these weights for any odd value, if

there is such odd value apply the rejection rule, then obtain the average weight of

the trusted weights

7. Use the average weight to calculate the density of the distilled water at the

designated temperature.

8. Compare the obtained density value with the literature (reference) values using the

following linear regression equation of water density with the temperature range

25 to 50 oC.

Each group will perform the experiment at a SPECIFIC

temperature within the temperature range 25 to 50 oC.
 Measurement of Density 17

Lab # 1: Data Sheet and Calculations

Name_________________ Date_________________ Lab section________

A) Total Volume of the bottle with its cover _______________ mL

B) Mass (m) of the empty bottle and its cover _______________ g

C) Mass (m) of liquid at _________ oC is given by:

Trial #1 Trial #2 Trial #3 Trial #4 Trial #5

m(Bottle + liquid) ________ g _________ g _________ g _________ g _________ g

m(liquid) ________ g _________ g _________ g _________ g _________ g

Rejection Rule:
_____________________________________________________________________

_____________________________________________________________________

Average mass of Liquid after applying the rejection rule (if needed):
m = ___________ ± ____________ g

D) Density of distilled water = _________ ± _________ g/ml at _________ oC

E) Reference Density of water = _________ g/ml at _________ oC

F) The % error = _________

G) Exchange your group result of density with other groups and list these values
below. Also plot the densities of the distilled water versus temperature using excel
graph and identify the linear regression of the plot. Finally, compare the linear fit
slope and intercept with the reference values and comment on any deviation or
error.

Group Distilled Water Density (g/mL) Temperature (oC)

A

D
18 Error Analysis & Home Work

DATA TREATMENT: HOMEWORK PROBLEMS

1. The volume of a cylindrical capillary tube is given by the expression V = r2h,

where r is the radius of the capillary and h is the height. If the radius of the
capillary is found to be 0.030 cm with error limits  0.002 cm and the height is
found to be 4.0 cm with error limits  0.1 cm, what is the volume of the
capillary tube and its limits of error?

2. The molar mass of a vapor is determined by filling a bulb of known volume

with the vapor at a known temperature and pressure and measuring its mass
(Dumas method). If the vapor is assumed to be ideal, then from the ideal gas law

M = mRT/PV

where M is the molar mass, m is the mass of the vapor, R is the gas constant,
T is the temperature, and V is the volume of the bulb. Using the following data:

m = 1.0339  0.007 g
T = 274.0  0.5 K
P = 1.036  0.001 atm
V = 0.1993  0.0001 l
R = 0.08205 L atm K-1 mol-1

determine the molar mass and its limits of error.

3. a) Graph the following points and determine the slope and y-intercept of the
best straight line through them:

X Y
1.8 0.4
3.2 3.5
3.9 6.6
5.1 9.7
5.8 12.8

(b) Determine the best slope and y-intercept of the above points by the method
of least squares. Compute an estimate of the standard deviation in the slope
and intercept.
 Measurement of Density 19

4. In part I of the experiment on EMF of Electrochemical cells, two groups of

students measured the temperature variation of the cell

Cd(s)  Cd2+ (aq,c), SO42- (aq,c)  Cd(Hg,x2)

and obtained the following results:

GROUP A GROUP B
Temp. (C) EMF (mV) Temp. (C) EMF (mV)
2.2 61.8 2.0 58.7
15.3 64.2 15.0 61.6
26.0 66.4 24.5 62.6
35.4 68.1 35.0 64.8

(a) Plot the EMF versus temperature for the cell for both groups. Note that the
slope is equal to (E/T)P.
(b) Use linear regression to calculate the EMF of the cell at 25C for both
groups.
(c) Calculate the limits of error in the EMF at 25 C for both groups.
(d) Calculate G from equation (1) and its limits of error for both groups.
(e) Repeat the above for S using equation (4) and H using equation (5).
(f) Report H and its limits of error to the correct number of significant
figures for group A and group B.
(g) Comment on the accuracy of the results for the two groups.

Equations:

G = -nFE (1)

G = G + RT ln Q (2)

RT
E  E  ln Q (3)
nF

E
S   nF (  T ) P (4)

H  G  T S (5)
 21

CONDUCTIVITY OF STRONG AND

WEAK ELECTROLYTES

Objectives:

1. To determine the electrical conductivity of KCl and acetic acid solutions.

2. Determine the limiting conductivities for the two solutions.

3. To determine the dissociation constant of acetic acid.

Theory:

Substances that are caused to dissociate into ions by the effect of suitable solvents
conduct electric current. The resistance, or its reciprocal the conductance, of these
solutions therefore depends on the degree of dissociation and the concentration of ions
The specific conductance or electrical conductivity, , is the conductance of a cube of
a solution contained between two parallel electrodes 1 cm square and 1 cm apart.

 = G x (l/A) (1)

where G is the conductance, the SI units of which is the Siemens (S=-1), and l is the
length of the material and A is the cross-sectional area.  has units of  -1 cm -1
(S cm-1 ). Owing to the high dependence on concentration, however, conductivity
does not represent a suitable measure for comparison between electrolyte solutions.
A better measure for this purpose is the equivalent conductivity or the molar
conductivity . This is defined as

 = /c (2)

where c is the concentration in mol/cm3.

In the case of infinite dilution (c  0), the molar conductivity  tends towards a
particular limit value called the limiting molar conductivity o , which can be
expressed as the sum of the limiting molar conductivities of the separate ions.

 o  o  o (3)

(The values for the molar conductivities of most ions at infinite dilution are tabulated
in the handbooks).
22 Conductivity of Strong & Weak Electrolytes

STRONG ELECTROLYTES

Strong electrolytes (KCl) are found to obey the Debye-Hückel-Onsager equation

  o  a c (4)

where a is a constant.  for strong electrolytes can be found from the intercept of
the plot of  against c .

WEAK ELECTROLYTES

For weak electrolytes the concentrations at which the molar conductivity has reached
their limit value are very much smaller than that for strong electrolytes. So, in the case
of weak electrolytes, precise measurement of limiting molar conductivity is not
possible through extrapolation from the molar conductivity-concentration curve.
According to Arrhenius theory, the degree of dissociation  for a weak electrolyte is
given by

 = /0 (5)

The equilibrium constant for a weak acid can be determined from .

HA = H + A- (6)

c 
Ka  (7)
(  )
Substituting for 

c(/ o ) 
Ka  (8)
(  / o )

c
 (9)
o (  / o )

c
Ka  (10)
 o ( o  )

Cross multiplication gives

 Conductivity of Strong & Weak Electrolytes 23

K a o  K a  o   c (11)

dividing the equation by K a o 

  c
  (12)
 o K a o

 c 
  (13)
 Ka   o
o
From a plot of 1/ versus c we can find the equilibrium constant and .

Experimental Procedure:
1. All glassware must be very clean to get good results. Rinse all glassware
with distilled water, then at least two times with conductance water, before
preparing the solutions. Similarly the conductance cell must be rinsed at least
two times with conductance water. The measured conductance of this water
should be less than 5x10-6 -1.

2. Prepare 250.00 mL of each of the following solutions by suitable dilutions,

using conductance water, starting from stock solutions of 1.00 M KCl and
1.00 M acetic acid: 0.1 M, 0.05 M, 0.01 M, 0.005 M, 0.001 M, 0.0005 M,
and 0.0001 M.

3. Fill the clean conductance cell with conductance water, and place in the
temperature bath operating at 25C. Measure the conductance after
5 minutes. To do this connect the cell to the conductance bridge, set the
temperature dial to 25C, and set the cell constant to the appropriate value,
and then read off the conductance from the digital display.

4. For each solute, measure conductance of all the solutions, beginning with the
most dilute. (Rinse the cell several times with a small amount of the solution
to be measured before filling it with that solution). It is very important to
check the cell constant before each reading.  (water) must be subtracted
from all measurements!
 24 Conductivity of Strong & Weak Electrolytes

Report:
The value read off the conductance bridge is the conductance for one cubic centimeter
of solution, when the appropriate cell constant is set in the meter. Note that the 
values should be corrected for  H2 O .

PART l:

For strong electrolyte (KCl):

1. Plot the molar conductivity of KCl against c . Note that c should be in units
of mol cm-3.

2. Calculate  for KCl from the Y-intercept.

3. Compare this value with the literature value.

PART 2:

For weak electrolyte (acetic acid)

1. Plot the reciprocal of the molar conductivity,1/, of acetic acid solution

against c().

2. Calculate Ka for the dissociation of acetic acid from the slope.

 obtained from the Y-intercept is usually imprecise and therefore it is
advisable not to use it in the calculation of Ka from the slope but instead to
use the literature value for .

3. Note that the Ka value so determined has the unit of mol cm-3 . Change its
unit to mol L-1 then compare it with the literature value.

References:

1. Shoemaker, D. P., Garland, C. W., Steinfeld, J. I., and Nibler, J. W.,

Experiments in Physical Chemistry, 5th Edition, McGraw-Hill, N. Y., 1989.
Experiment no. 17, pages 253-267.

2. PHYWE University Laboratory Experiments in Chemistry. pages 3.6.1

 25

TRANSFERENCE OF IONS BY THE MOVING

BOUNDARY METHOD

Objectives:

1. To determine the transport number of H+ and Cl- ions.

2. To determine the mobilities of the H+ and Cl- ions.

Theory:

The transference number Ti of ion i in a solution is defined as the fraction of the

electric current carried by that ion. The moving boundary method is one way of
measuring Ti. The apparatus used in this experiment is similar to that shown in the
figure.

ch arg e (ch arg e per ion)  (number of ions)

current   and
time time

(number of ions) (concentration  area  length)


time time

the current carried by ion i is

F zi ci l A
Ii  (1)
t
where,

F = 96487 Coulomb/mol
zi = charge on ion i
ci = molarity of ion i
A = area of the tube
l = average distance which the ions move in time t.

If the total current is I, which is equal to ( I+ + I- ) then by the definition of transference

number,
26 Transference of Ions / Moving Boundary Method

F | z |c l A
Ii i i
Ti = = (2)
I It
The velocity vi of ion i is l /t , so (1) can be written

I i  F zi ci A vi (3)

The velocity of an ion in an electric field is proportional to the strength of the electric
field E:
vi  E
vi = ui E (4)

where the proportionality constant ui is called the ionic mobility. Then substituting
into (3),

I i  F zi ci A uiE (5)

In a solution of MX, representing the cations by + and the anions by -,

I  I  I

 F z  c A u E  F z  c  A u E (6)

and because z   z  and c  c substituting equation (6) into equation (2) gives

I u
T     (7)
 ( I  I ) (u  u )
   
The ionic conductivity  i of an ion is given by

 i  ui F (8)

and the equivalent conductivity for an ionic solution is the sum of the ionic
conductivities,

     (9)

Substituting equation (8) into equation (9) one gets

  F ( u  u ) (10)
or
 Transference of Ions / Moving Boundary Method 27

( u  u )   (11)
F

In the experiment T , the transference number for H+ (aq), will be determined for
H
an HCl solution, and using the known value for the equivalent conductivity of
aqueous HCl, u and u the ionic mobilities of H  and Cl  , will be found.
H Cl 
Referring to the figure, the upper electrode in the apparatus is an Ag-AgCl electrode
(-) and the lower electrode is a Cd metal (+). The electrode reactions are

Anode : Cd(s)  Cd2+ (aq) + 2e-

Cathode : AgCl(s) + e-  Ag(s) + Cl-(aq)
Net : Cd(s) + 2AgCl(s)  Cd2+(aq) + 2Ag(s) + 2Cl-(aq)

The tube is filled initially with HCl(aq). When the current is passed through the
solution, the H  ions move towards the upper (negative) electrode, and the Cl ions
move towards the lower (positive) electrode. The moving ions carry the current
through the solution. The Cd  2 ions produced at the anode also move upward.
A sharp boundary forms between the HCl and CdCl2 solutions. To aid in seeing the
boundary, methyl orange indicator is added to the acid; then the acid layer is red, and
the CdCl2 layer is yellow. The boundary moves upwards in the tube at the average

velocity of the H  ions.

Experimental Procedure

1. Prepare the Ag-AgCl electrode by electrolysis of 1 M HCl; use the Ag

electrode as anode (+) and a Pt electrode as Cathode. Set the power supply to
about 2 V, and let the reaction proceed for about 10 minutes.

2. Prepare 200 ml of 0.100 M HCl by dilution of 1.000 M solution. Include 10

ml of methyl orange solution in the volumetric flask during the dilution. Fill
the apparatus with the 0.100 M HCl. Partially unscrew the Cd electrode at
the bottom, to fill the tube with solution; make sure that there are no air
bubbles in the tube. Turn on the thermostat-circulator, which is set at 25 C.
28 Transference of Ions / Moving Boundary Method

3. A milliammeter is used to measure the current. A white paper placed behind

the tube will make the boundary easier to see.

4. Turn on the high voltage DC power supply, and adjust the voltage to get a
current of 3.00 mA. As the reaction proceeds, HCl in the tube is replaced by
CdCl2 which has a larger resistance. Thus, it is necessary to adjust the
voltage frequently, to keep the current constant at 3.00 mA. Measure the
time needed for the boundary to rise 2.00 cm; repeat this measurement at
least two more times.

5. Repeat the experiment using currents of 4.00 mA and 5.00 mA.

 Transference of Ions / Moving Boundary Method 29

Report

1. Determine the average time needed for the boundary to rise

2.00 cm at each amperage. Using these average times in equation (2),
calculate the transference number of H  ion at each amperage. (Note the
diameter of the tube posted on the apparatus.)

2. For 0.100 M HCl,  = 3.913x10-2 S m2 mol-1. Using the average value for
the transference number of H  ions , calculate the ionic mobilities of
H  and Cl  from equations (7) and (11).

3. Compare the values obtained with the literature infinite dilution values and
comment on the difference. If ionic mobilities are not given in the literature
calculate them using equation (8) and the ionic conductivity values of
H  and Cl  . Discuss briefly the differences found between the values of
u H  and u 
Cl

Reference

John A. Dean, "Lange's Handbook of Chemistry", 13th edition, page 6-34, McGraw-
Hill Book Company.
 31

EMF OF ELECTROCHEMICAL CELLS

Objectives:

1. To determine the temperature dependence of EMF and to calculate the

thermodynamic functions, G , S , and H of the cell/reaction.

2. To determine the equilibrium constant Kc from EMF measurements.

Theory:

Electrochemical measurements are the most accurate method for measuring

thermodynamic properties such as G, S and H of reactions and activities of ionic
solutes.

Electrical work = charge  voltage

Joule = coulomb  volt

For the system acting as a battery, this gives:

G = -nFE (1)

where n is the number of moles of electrons that pass through the circuit per mole of
reactants, F = Faraday = charge on one mole of electrons = 96485 C/mol e -, and E is
the voltage in Volts.

G depends on the activities of the products and reactants as given by the equation

G = G + RT ln Q (2)

Where Q is the activity quotient. This leads to the Nernst equation

RT
E  E  ln Q (3)
nF

Since G = -nFEo, by using a potentiometer, which draws a negligible current, we

can measure the value of E.

By measuring the cell voltage at several different temperatures, we can determine the
entropy change from the relation.
32 Electrochemistry (E.M.F.)

S  nF (  TE ) P (4)

We can then obtain the enthalpy change from the relation

H  G  T S (5)

Part I: Temperature Dependence of EMF

In this part of the experiment the following electrochemical cell is studied:

Cd(s)  Cd2+ SO42- (aq,c)  Cd(Hg,X2)

The net change accompanying the passage of 2 Faradays of positive electricity

through the cell is given by
Cd (s) = Cd (Hg,X2)

Where the half-cell reactions are

Anode : Cd(s) = Cd2+ (aq,c) + 2e-

Cathode: 2e- + Cd2+ (aq,c) = Cd(Hg,X2)

In the above, (s) refers to pure crystalline solid, (aq,c) refers to an aqueous solution of
concentration c, and (Hg,X2) refers to an amalgam of Cd in Hg when the mole
fraction of Cd is X2.

From the EMF of this cell and its temperature coefficient, the changes in free energy,
entropy, and enthalpy for the above change in state can be determined, using the
equations developed earlier.

Procedure:
1. The cell is set up as shown in Figure 1. The Cd metal electrode (actually freshly
deposited Cd on a platinum wire ) is prepared by electrolysis of a 0.1 M CdSO4
using a 1.5-V dry cell with the platinum wire connected to the negative and a
Cadmium rod connected to the positive terminal. Exercise care to avoid the
flaking off of the deposited cadmium and keep the electrode wet at all times. As
shown in figure 1, the amalgam electrode (an amalgam is a solution of a metal in
mercury) is slowly attacked by oxygen in the solution, and must also be freshly
made.
 Electrochemistry (E.M.F.) 33

It was previously prepared as follows: The Cd is cleaned with sulfuric acid to

remove the oxide coating and washed with distilled water, cleaned & dried. The
cleaned Cd is then dissolved in the appropriate mass of triple distilled mercury.
Simply add a few drops of the amalgam solution to the "J tube" of this electrode.

Fig.1 Cadmium Amalgam Cell

2. Place your cell in a water bath; when it has come to thermal equilibrium, measure
the EMF, using the multimeter. Measure the EMF at four different temperatures,
ranging between 0 and 40C.

E
3. From a linear least squares fit of E versus T determine (  T ) P .

4. Using the fit from step 3 determine the EMF at 25C.

5. Calculate G, S, and H of the cell reaction at 25C using equations 1, 4, and 5.
A large deviation in the H value relative to the literature
H, value may be encountered since it is the sum of two large quantities (G and
TS) of opposite sign. This may be demonstrated through a propagation of error
analysis, cf. problem (4) on page 18.
34 Electrochemistry (E.M.F.)

6. Determine the mole fraction of Cd. Calculate G using the relation
G = G + R T ln Xcd assuming that, acd = Xcd then explain why G is not
equal to zero as would be expected when the standard state is Xcd = 1.

Part II: Determination of Equilibrium Constant

We will study the reaction:

Ag  (aq)  2 NH 3  Ag (NH 3)  (aq)

2

The equilibrium constant K is given by

a
Ag(NH 3) 
2
K  (6)
a  a 2NH
Ag 3

The activity coefficients of Ag  and Ag (NH 3)  ions are essentially equal, and the
2
activity coefficient of the neutral NH3 is unity. Thus, we can approximate K as Kc.

Ag (NH 3) 2
Kc  2
(7)
Ag  NH 3

For silver electrode in a solution containing Ag  (aq) .

Ag  Ag  (aq)  e 

The electrode potential is given as:

E  E o  RT ln aAg+ (8)
F

Your electrochemical cell is of the type:

Ag Ag  Ag  Ag
(c1) (c2 )

From equation (8) the EMF of the cell is given by

 Electrochemistry (E.M.F.) 35

Ecell = Eelectrode-2 - Eelectrode-1

=  E + RT ln(aAg+ )2  -  E + RT ln(aAg+ )1 
F F

( a Ag  ) 2
Ecell = + RT ln (9)
F ( a Ag  ) 1

Instead of activities, we will use molarities in our calculations.

Procedure:

1. Prepare the following cell as shown in Fig. 2.

Fig 2: Concentration Cell for the Demonstration of Equilibrium Constant with

Transference

2. We have a stock solution of 0.0500 M AgNO3 . For solution (1), use 10.00 ml of
this solution + 10.00 ml of the NH3 solution. Calculate the initial molarities of the
silver ion Ag+ and NH3 that is NH3 in the solution. We will measure the
36 Electrochemistry (E.M.F.)

EMF of this cell with several different concentrations of Ag  in solution (2).

Prepare 0.0100 M, 0.00300 M, and 0.00100 M solutions by dilution. Use 20.00 ml
of each of these solutions in the beaker for solution (2).

3. Measure the EMF of the cell with these three different solutions.

4. Calculate Ag+1 for each solution from equation (9). This value will be taken as
the equilibrium concentration of Ag+ ion Ag+1 in equation (7).

5. The Ag(N H 3) 2  complex has a high formation constant Kc and the reaction
almost goes to completion at the end, therefore, as a good assumption the
equilibrium concentration of the complex,  Ag(N H 3) 2   can be considered to
equal to the initial concentration of the silver ion Ag+0 .

6. From the stoichiometry of the reaction, the equilibrium concentration of

ammonia NH3 is:

NH3 = NH3 - 2  Ag(N H 3) 2  

7. Calculate the average value of Kc from the three runs.

8. Compare Kc with the literature value.

Reference:

1. D. P. Shoemaker, C. W. Garland and, & J. W. Nibler, "Experiments in Physical

Chemistry", 6th Edition, McGraw Hill, New York (1989). Pages 238-240.
 37

DIFFUSION POTENTIAL

Objectives:

1. To determine the factor (RT/F) from potential diffusion measurements by

using a cation permeable membrane.

2. To determine the transport numbers of cations and anions by using a

cellophane membrane.

Theory:

In general when two electrolyte solutions of different concentrations are separated by

a membrane, there will be an electric potential difference across the membrane. This
potential difference is known as the Nernst potential. The effect of this potential
difference is to prevent the crossing movement of more ions of the permeable type
across the membrane from high concentration side into the low concentration side.

Fig. Two cubic cells separated by a membrane

The Gibbs energy difference, Ge arising from the potential difference, , is

Ge = z F (1)

where z is the charge on the permeable ions (z = 1, in our case),while the Gibbs
energy arising from the concentration difference is

c
Gc  RT ln ( 2 ) (2)
c1
At equilibrium G = 0, and therefore
38 Determination of Diffusion Potential

 G   G e   Gc  0
or
c
zF + RT ln ( 2 ) = 0
c1
thus
RT c
 = ln ( 1 ) (3)
zF c2

The cations and anions of the electrolyte generally have different velocities, the faster
ionic species initially diffuse first; the separation of the charges results in a potential
difference, which is called diffusion potential D and is given as:

D = (t- - t+) (4)

where, t+ and t- are the transport numbers of the cations and anions, respectively.

Substituting  in equation (3) into equation (4), one obtains

RT c
D = (t--t+) ln ( 1 ) (5)
zF c2

In reality, the concentrations should be replaced with the activity of the ions, thus:
RT a
D = (t-- t+) ln ( 1 ) (6)
zF a2

The sign of the potential depends on which ionic species has the higher velocity.

Part-I:
When the membrane is permeable to one type of the ions only, the transport number
of the diffused ion is zero i.e. , t+ or t-=0 In case of cation permeable membrane we
have:
t- = 0

Accordingly, equation (6) becomes:

D = -

RT a
=- ln ( 1 )
zF a2

RT a
D  ln ( 2 ) (7)
zF a1

Plotting D vs ln (a2 /a1) gives a straight line with a slope equals to (RT/zF).
 Determination of Diffusion Potential 39

Part-II

For permeable membrane that permit both positive and negative ions to be diffused
from the more concentrated side, the value of D is given by equation (6). One of
the most known applications of the measurement of the diffusion potential is the
determination of the transport number of each ionic species. since,

t+ + t- = 1 (8)

From equation (6) and (8) t+ and t- can be determined.

EXPERIMENTAL PROCEDURE

Part-I: Using a cation permeable membrane.

1. From 0.10 M KCl (given) prepare by dilution 0.01 M KCl/250 mL, and from the
diluted one (0.01 M KCl) prepare 0.001 M KCl/250 mL using the suitable
volumetric flasks.

2. Place the cation permeable membrane on the large opening of one half of the
Ussing chamber. Place the second half on top and screw the two parts tightly
together.

3. With the aid of a 100 mL beaker and the available glasswares,fill into a half of the
Ussing chamber, exactly, 90.0 mL of the 0.001 M solution and to the second half
about 100.0 mL of 0.01 M KCl solution.

4. Place a magnetic stirrer bar in the half containing the 0.001 M KCl solution.

5. Measure and record the asymmetry potential of the electrodes in the cylinder with
1.00 M KCl ( zero ). Like  H2 O in the conductivity experiment, the asymmetry
potential should be deducted from all the future D readings.

6. Immerse the electrodes (rinsed and dried) in the measurement solutions, and
measure D.

Hint: Connect the electrode in 0.01 M KCl to the earth socket. Allowing a few
minutes for the potential ( 50 mV ) to become established.
40 Determination of Diffusion Potential

7. For the 0.001 M KCl solution introduce the following portions from 1.00 M KCl
solution using graduated pipette: 5 portions of 0.1 mL, followed by 3 portions of
0.2 mL, and then 5 portions of 1.0 mL.

8. Measure D per each portion after stirring the solution carefully with the aid of
a magnetic stirrer for about 30 seconds.

9. Record the temperature of the tested solution in your data sheet plus the data
collected from steps 5 to 8.

10. Remove the permeable membrane from the cell and keep it in distilled water dish;
and rinse out the Ussing chamber thoroughly with distilled water.

Part-ll: Using a cellophane membrane.

1. Stretch moistened cellophane film over the opening of the screwless part of the
Ussing chamber and leave to dry. Place the second half on top, push the screws
through the film and screw the two parts tightly together.

2. Fill the two halves of the Ussing chamber, as far as possible simultaneously, with
about 100 mL of 0.01 M and 0.001 M HCl solution. Immerse the electrodes
(rinsed and dried) in the measurement solutions for about 15 seconds and
determine the diffusion potential (mean value).

Hint: (using the electrode connected to the earth socket to the multimeter for the
low concentration).

3. Return the electrodes to the cylinder of 1.00 M KCl, check and record the
asymmetry potential.

4. Repeat the last two steps twice at intervals of about 2 minutes.

5. Use a thermometer to determine the temperature of the solution under study.

 Determination of Diffusion Potential 41

REPORT: Part 1

1. The concentration c1 is changed by addition of 1.00 M KCl portions. In this

case

co Vo  c x Vx
c1  (9)
Vo  Vx
where
co = 0.001 M starting concentration
Vo = 90.0 mL starting volume
cx = 1.00 M concentration of the added solution in portions
Vx = total volume added in portions
2. Using data from Table 1, plot a calibration curve of the activity coefficient, f,
versus concentrations of KCl. The activity coefficients could be fitted to a fourth-
degree polynomial

f  0.9477  3.211 c  15.64 c 2  28.73 c 3  15.97 c 4 (10)

Tabulate the f1's by substituting the values of c1's calculated from Eq. (9) into
Eq. (10). Then tabulate the a1's obtained by multiplying f1's by c1's.

Table 1: Activity coefficient, f.

c(mol/L) HCl KCl

0.001 0.9656 0.9652
0.002 0.9521 0.9520
0.005 0.9285 0.9274
0.010 0.9043 0.9022
0.020 0.8755 0.8706
0.050 0.8304 0.8182
0.100 0.7964 0.7707
0.200 0.7667 0.7200
0.500 0.7571 0.6552
1.000 0.7090 0.6110
42 Determination of Diffusion Potential

3. Plot D against ln (c2/c1) and ln (a2/a1). Comment on the which plot gives a
better linear fit.

4. Plot D versus ln (a2/a1) and use the linear regression analysis to determine the
slope and the intercept. The slope is given by -RT/F. Thus the factor (RT/F) can
be determined from the experiment.

5. Since

R = 8.314 JK-1 mol-1

F = 96485 C
T = (t + 273.15)K

You can determine the factor, (RT/F), theoretically. Compare the two values
and calculate the percent error. It is important to note that (RT/F) is a
fundamental factor in physical chemistry.

REPORT: Part 2

1. Correct the D values for each of the three measurements on the HCl solutions
for the asymmetry potential.

2. Obtain an average of the three D value.

3. Calculate the transport numbers, t+ and t- using Eqs. (6) and (8).
4. Note that one expects t+  t- because H+ ions are expected to carry most of the
fraction of the electric current.

Reference:

"PHYWE, University Laboratory Experiments CHEMISTRY", page 3.6.3.

 43

KINETICS OF THE HYDROLYSIS OF

ETHYL ACETATE WITH HYDROXIDE ION

Objective:

To determine the rate constant for the reaction of ethyl acetate with hydroxide ion.

Theory:

This experiment is an investigation of the rate of the saponification reaction of ethyl

acetate with hydroxide ion

CH3COOC2H5(aq) + OH-(aq)  CH3COO-(aq) + C2H5OH(aq) (1)

This reaction is first order with respect to each reactant, and thus second order overall.
EA and OH- are the molarities of ethyl acetate and of hydroxide ion at time t, and
EA and OH- are the initial molarities at t=0 .

When EA = OH-, then EA = OH-, and the rate law gives

1  1  kt (2)
[ EA ] [ EA ]o

where k is the rate constant for the forward reaction.

When EA  OH-, the rate law for this reaction gives

[ EA] [ OH  ] o
ln{ 
}  {[ EA]o  [ OH  ]o } k t (3)
[ EA ] o [ OH ]

The concentration of the hydroxide ion OH- can be measured at any time by
removing an aliquot from the reaction mixture, adding it to excess HCl to stop the
reaction by consuming the unreacted OH-, and back titrating with standard NaOH
solution. By studying the variation of the OH- as a function of time t, the rate
constant k of this reaction can be determined.
44 Kinetics of Ethyl Acetate with Hydroxide Ion

Experimental Procedure:

1. Standard 0.020 M solutions of ethyl acetate, sodium hydroxide and hydrochloric

acid will be provided.
2. As shown in Table 1, two runs (A and B) will be done,

3. For run A, the concentrations of the sodium hydroxide and ethyl acetate solutions
are equal, while for run B they are not.

4. For each run, measure the indicated amount of NaOH solution, H2O and ethyl
acetate solution into the appropriate flasks (labeled REACTION FLASK A, B and
TEMPORARY FLASK A, B). Place all the flasks, with weights, into the water
bath.

5. Eight samples will be taken from each run to measure the progress of the reaction.
Place in each of eight conical flasks marked A1 - A8 (for run A) or B1 - B8 (for
run B) one drop of phenolpthalein and 10 ml (using a pipette) of 0.020 M HCl.
Addition of one of the above samples to the appropriate flask will serve to stop the
reaction.

TABLE 1

Run Reaction Flask Temporary Flask

NaOH H2 O Ethyl Acetate
A 100 mL - 100 mL
B 100 mL 50 mL 50 mL

6. To start a run, introduce a magnetic bar into the reaction flask, then place it on the
magnetic stirrer, and add the solution from the corresponding temporary flask
while stirring vigorously. Return the reaction flask to the water bath. To measure
the progress of the reaction, pipet a 20.00 ml sample from the reaction flask and
pour into the appropriate conical flask after 5, 10, 15, 20, 30, 40, 50, 60 minutes. It
takes about 0.4 minute for the 20-ml pipet to drain. Thus, let the pipet start to
drain into the appropriate conical flask, containing excess HCl, about 0.2 minute
before the desired time. Mix thoroughly.

7. Back titrate each sample with standard NaOH (0.020 M) and record the volumes
required. Record the temperature of the bath. The instructor will divide the
 Kinetics of Ethyl Acetate with Hydroxide Ion 45

students in two groups, each to carry only one run A or B, and then exchange the
data at the end of the experiment, in order to have the result for both runs.
TABLE 2

STEP TIME (Min) ACTIVITY

RUN A RUN B
1 Start Timer
Mix run A Mix run B
2 5 A1 B1
3 10 A2 B2
4 15 A3 B3
5 20 A4 B4
6 30 A5 B5
7 40 A6 B6
8 50 A7 B7
9 60 A8 B8

Report:

1. Record the molarities of the ethyl acetate, NaOH and HCl standard solutions.

2. To calculate OH- at different times for each run, let V (HCl) be the volume of
HCl (10.00 mL), and let V (OH-) be the volume of NaOH used in the back titrtion.
At the equivalence point,

No. of moles of acid = No of moles of base

V(HCl)xM(Std HCl)=V(OH-)xM(Std OH-)+(20.00mL)x[OH-] (4)

Since the aliquots from the reaction are always 20.00 mL. Solving
for OH-:

{ V (HCl)  M (Std HCl)  V (OH  )  M (Std OH  ) }

[ OH  ]  (5)
20.00

From the reaction stoichiometry,

[ OH  ]o  [ OH  ]  [ EA]o  [ EA] (6)

so [EA] can be calculated. Make a table showing reaction time,

V(OH-), [OH-] and [EA] for each run.
46 Kinetics of Ethyl Acetate with Hydroxide Ion

3. Using equation (2) for run A, plot 1 versus t and determine the rate constant
[ OH  ]
k from the slope, (Here k = slope).
[ EA ][ OH  ]o
4. Using equation (3) for run B, plot ln{ } versus t and calculate k from
[ EA ]o [ OH  ]
the slope, (Here k  slope).

5. Compare the average value of the rate constant for the two runs with the literature
value.

Reference:

C. H. Banford and C. F. H. Tipper, "Comprehensive Chemical Kinetics", Vol. 10,

p. 169.
 47

KINETIC STUDY USING SPECTROSCOPY

Objectives:

1. To determine the order of the reaction of crystal violet with hydroxide ion.

2. To determine the rate constant of the reaction.

Theory:

(CH3)2N (CH3)2N

+ - HO C N(CH3)2
C N(CH3)2 + OH

(CH3)2N (CH3)2N

(Violet) (Colorless)

This reaction can be written as:

_
CV+ + OH CVOH
(1)

The rate of this reaction depends upon CV+ and OH-, and the rate law is of the form:

 d [CV  ]
 k [ CV  ]m [OH  ]n (2)
dt

2
d [CV  ] 2

1 
[CV ] m
  k [ OH  ]n
1
dt (3)
48 Kinetics Using Spectroscopy

If m = 1, integration gives:

[CV  ]
ln{ 2   k [ OH  ]n ( t  t ) (4)

[CV ]
2 1
1

A spectrophotometer can be used to follow the progress of this reaction by

measuring [CV+] as a function of time. Recall the Lambert-Beer law,

A  [CV+]

A   l [CV  ]  log ( 100 ) (5)

10 % T
or
l[CV+] = log10 (100) - log10 (%T) = 2 - log(%T) (6)

where, A = absorbance

%T = percent transmittance
 = molar absorptivity
l = path length

It is assumed that CV+ is the only solute present which absorbs radiation at the
wavelength used in the experiment. To obtain a reasonable absorbance A, the initial
[CV+] should be less than 10-5 M. To get reaction rates which are suitable for
convenient measurement, [OH-] should be about 0.1 to 0.01 M. Thus with the initial
[CV+]  [OH-], the [OH-] is essentially unchanged by the reaction and can be
treated as a constant. Substitute for [CV+] from equation (6) into equation (4)

[ 2  log (% T ) ]
ln{ 10 2 }   k [ OH  ]n (t  t ) (7)
[ 2  log (% T ) ] 2 1
10 1

Thus, if the reaction is indeed first order in the crystal violet, a plot of
ln[ 2  log10 (%T )] versus time should be a straight line with slope equal to
 k [ OH  ]n .
 Kinetics Using Spectroscopy 49

For two experiments (a and b) having different concentrations of OH- and the same
concentrations of CV+ the slopes, are:

slope a   k [OH  ]n (8a)

a

slope b   k [OH  ]n (8b)

b
Taking the ratio,

[ OH  ]
{ b }n  ( slope b) (9)
[ OH  ] ( slope a )
a
By taking logarithms:


[OH ]
n log{ b }  log ( slope b) (10)
[OH ] ( slope a )
a
All quantities except n are known, so (10) can be solved for the value of n, the order
of the reaction with respect to the hydroxide ion. Finally, the slope of the
ln[2-log(%T)] versus T plot may be used to get the rate constant k. The six plots will
six k values that are then averaged.

ADDITIONAL NOTES

It is not necessary to know the actual value of [CV+] in any of the calculations. When
the slope of the graph of ln[ 2  log10 (%T )] versus time is found, the "ratio" of two
crystal violet concentrations from the same run is being used, as indicated in equation
(5). Provided the Beer-Lambert law is valid in the range of concentrations used, the
factor to convert from [CV+] to absorbance cancels in this ratio. The only concern
with the actual [CV+] is that the initial concentration should be such as to give a good
range of %T values during the run. For best accuracy in analyzing the data, the %T
values should be in the range of 20% to 80%. The appropriate crystal violet solution is
about 1x10-5 M.

The rate of reaction (1) of course depends upon temperature. In order to keep the
experimental set-up reasonably simple, the reaction mixture is not thermostatted.
Thus, values of [OH-] are used so as to give a reasonable range of data in a run of only
5 to 10 minutes; the temperature should remain constant during this interval.
50 Kinetics Using Spectroscopy

Reaction (1) is reversible, as most reactions are. At equilibrium,

[CVOH ]
K (11)
[CV  ][OH  ]

At 25C, K for this reaction is 0.260 Lit mol-1 s-1. With the concentrations that are
used in this experiment, [CV+] at equilibrium will be about 10-9 M, which corresponds
to more than 99% transmittance. Thus, if the measurements are stopped when %T is
between 80% and 90%, the rate of the reverse reaction is still negligible.

EXPERIMENTAL PROCEDURE:

1. The instrument has to be adjusted to 590 nm many other parameters to get kinetic
scans successfully.

2. Fill the cuvette with distilled water, wipe out any finger prints using tissue paper
and place it in the sample chamber firmly. Then touch scan.

3. The six runs indicated in the above table will be done. For each run, clean and dry
the beakers to be used. Measure the indicated amounts of crystal violet solution
and water into the beaker 1 and measure the appropriate amounts of NaCl and
NaOH solutions into the beaker 2.

PREPARATION SETUP

RUN BEAKER 1 BEAKER 2

CV+ H2O 0.1 M NaOH 0.1 M NaCl
1 10.00 mL - 10.00 mL -
2 6.00 mL 4.00 mL 10.00 mL -
3 4.00 mL 6.00 mL 10.00 mL -
4 10.00 mL - 6.00 mL 4.00 mL
5 6.00 mL 4.00 mL 6.00 mL 4.00 mL
6 4.00 mL 6.00 mL 6.00 mL 4.00 mL

4. Pour beaker 1 solution into beaker 2 and start the timer, quickly fill the mixture
into the cuvette wipe off the finger prints and place it in the sample chamber,
(This activity is done in 30 seconds). The reaction is run for 10 minutes. Press
scan.
 Kinetics Using Spectroscopy 51

Report:

1. Make a data table that gives the values of ln[ 2  log10 (%T )] at one minute
intervals for each of the six runs. On two graphs, one for runs 1-3 and the other for
runs 4-6, plot ln[ 2  log10 (%T )] versus time. Since each of these groups has the
same [ OH  ] , the three lines on each graph should be parallel.

2. Use a least squares calculator program to find the slopes of the lines.

3. Using the averages of the slopes of the lines on the two graphs, determine the
reaction order with respect to [OH-] ion for each run using equation (10).

4. Evaluate the rate constant using equation (7), where the concentration of [OH -]
ion is assumed to be constant throughout the reaction.

5. Compare the experimental values with those in the reference.

Reference:

J.C. Turgeon and V.K. LaMer, J. Am. Chem. Soc., 74, 5988 (1952)
 53

KINETICS OF CANE SUGAR

(SUCROSE) INVERSION

Objectives:

1. To determine the specific rotation of cane sugar solution.

2. To determine the rate constant of the hydrolysis of cane sugar.

Theory:

Determination of specific rotation:

Some substances have the ability to rotate the plane of polarized light through a
certain angle. Substances which rotate the plane of polarization to the right are called
dextro-rotatory, those which rotate the plane to the left are called laevo-rotatory.
These substances are said to be optically active.

The specific rotation (rotatory power) of solutions of optically active substances is

defined as the angle through which the plane of polarization of sodium-D light (wave-
length  = 589.9 nm) would be rotated by a column of solution 100 mm in length,
t
containing 1 g of substance per cm3 at 20 C. It is expressed by the symbol   .

The specific rotation of cane sugar (sucrose) can be determined by measuring the
rotation of the plane of polarization through various sugar solutions of known
concentrations with a half-shade penumbra polarimeter. In Part I of this experiment
we will investigate whether the rotation angle  is proportional to the concentration, c
(c g sucrose in 100 g solution). The specific rotation at a known concentration c can
be determined from the rotation angle  at a known concentration:

   (1)
c

(related to a column length of 100 mm). The specific rotation  t will be determined
from the slope of the plot of the observed angle of rotation versus the weight percent
concentration c instead of Eq. 1.
54 Kinetics of Cane Sugar Inversion

In Part II the rate constant of the hydrolysis of cane sugar will be determined by using
the established result in Part I that the rotation angle  is proportional to concentration
c.

Kinetics of cane sugar inversion:

The hydrolysis or inversion of cane sugar in presence of hydrogen ions as catalyst is

an example of a first order reaction, although the mechanism is not unimolecular. In
presence of H+ ions, an aqueous solution of cane sugar breaks down into optically
active glucose and fructose.

H O
C12H22O11 3  C H O + C H O
  6 12 6 6 12 6

sucrose glucose fructose

If the reaction is first order, the rate constant k1 can be expressed by:

 d [A ]
 k [A]
dt

At d [A ] t
  k  dt
A0 dt 0

[A ]0
ln  kt (2)
[ A ]t

Where [ A]0 is the initial concentration of reactant, and [ A]t is the concentration of
reactant at time t after commencement of the reaction.

The progress of the reaction can be followed very easily by means of a polarimeter.
Cane sugar is dextrorotatory, whereas the mixture of glucose and fructose resulting
from inversion is laevorotatory. Thus a particular decrease in the concentration of the
cane sugar, due to inversion, will be accompanied by proportional decrease in the
optical rotation.
 Kinetics of Cane Sugar Inversion 55

Let  o ,  t and   be the observed angles of rotation of the plane of polarized light
at the beginning of the reaction, at any t and at the end of the inversion respectively.

The total change in rotation (  o    ) , therefore, will be proportional to the initial

concentration a o of cane sugar. Also, the change in rotation (  o   t ) by the time t
after commencement of the inversion is proportional to the decrease in concentration
of cane sugar by that time. Thus the concentration of cane sugar remaining at time t
will be proportional to:

( o   )  ( o  t )  ( t   )
i.e.
[ A]  (      )

[ A]t  (  t    )

Substitution of the above quantities into equation (2) gives:

(   )
ln   k t (3)
(   )
t 

(o   )
A plot of ln against t gives a straight line of slope equals the first order
( t   )
rate constant k1 .

Experimental Procedure:

Part I. Determination of specific rotation:

1. The solutions of sucrose in water containing 12%, 9%, 6% and 3% sucrose by

weight are prepared using the proportions given in the following table:

g Sucrose 12 9 6 3
g Water 88 91 94 97

2. Fill the sample cell with distilled water taking care not to trap any air bubbles.
Calibrate the polarimeter and record water. Take each of the stock solutions and
fill the sample cell, taking care not to trap any air bubbles. Immerse the cell in the
56 Kinetics of Cane Sugar Inversion

temperature bath which has been set at 30 C for 5 minutes. Wipe the glass
window dry with a soft tissue paper.

3. Measure the rotation angle  of the four solutions at 30 C with a half-shade

penumbra polarimeter in which light of wavelength 589.9 nm (Sodium-D) is first
plane-polarized by a polarizer and then studied by a second polarizer to find its
new plane of polarization after passing through the sample substance. Adjust the
two halves of the field in the polarimeter to identical brightness.

4. Note that in your set up light travels a distance of 200 mm while the
specific rotation is defined for a 100 mm path length.

Part II. Determination of rate constant:

1. Place the 24% stock solution and 2M HCl containers in a 30 C thermostated
water bath. Mix 25 mL of the stock solution (temperature 30 C) with 25 mL of
2M HCl (temperature 30 C). Start the stop clock (reading in minutes) as soon as
the solution is prepared. (Do not stop the clock until the experiment is over). Pour
the reaction mixture in the sample cell and place it in the polarimeter sample
holder. The sample cell is thermostated by placing it in the 30 C thermostated
water bath.

2. Measure the angle of rotation  t of the solution every five minutes. Take about 8
readings.

3. The  o is taken as the measured angle of rotation for the 12% sugar solution in
the first part of the experiment.

4. The temperature of the reaction will be raised to 70 C (Place the measuring tube
in the 70 C bath for about 5 minutes), in order to complete the hydrolysis. Then
bring the temperature back to the 30 C (Place the measuring tube in the 30 C
bath for about 15 minutes) and read the final angle of rotation   .

Report:

1. Remember to correct for water and divide all your angles of rotation by 2 since
the path length in your set up (200 mm) is twice that specified in the definition of
specific rotation (100 mm).
 Kinetics of Cane Sugar Inversion 57

2. Plot  (the angle of rotation for a path length of 100 mm) against the weight %
concentration c. (For the weight percent concentration c use 0.12, 0.09, 0.06 and
0.03 rather than 12, 9, 6 and 3%.) The slope of a linear fit of  vs. c is the specific
rotation at 30 C [  ] 30
exp .

3. Find the literature value of [  ] 20 for 12 g sucrose/100 g solution using the

relation

[  ]20  66.412  0.01267 d  0.00376 d 2

which is found on page E-425 of the “Handbook of Chemistry and Physics”

(edition 70) for 0 t0 50 g sucrose/100 g solution. The relative density, d is equal to
1.0465 (Ref: page D-264 of the above Handbook).

4. Calculate [  ] 30 using the equation (from the reference in step 3)

[  ]t  [  ]20 [ 1  0.00037 ( t  20 ) ]

Then compare [  ] 30
lit with [  ] exp from step 2.
30

5. The data and results for the reaction mixture may be combined in the following
table.


t
f*

(    )
* where f = l n
( t   )

6. From a plot of f versus t find k1 for sucrose inversion at 30C.

References:

1. "PHYWE, University Laboratory Experiments CHEMISTRY" pages 3.5.4.

2. Daniels, Williams et al. "Experimental Physical Chemistry"
3. 7th Edition, McGraw-Hill, pp. 149-152.
4. Handbook of Chemistry and Physics, 70th Edition, R. C. Weast (Ed.), CRC Press,
Boca Raton, (1989), p. E-425.
 59

ADSORPTION ISOTHERMS

Objectives:

1. To investigate the Langmuir and Freundlich isotherms for acetic acid/charcoal

system.

2. To determine the specific area for charcoal.

Theory:

The interaction between adsorbed molecules and solid surfaces varies over a wide
range from weak nonpolar van der Waal's forces (physisorption) to strong chemical
bonding (chemisorption).

An adsorption isotherm relates the amount of substance adsorbed on a surface ( solid

or liquid ) to its concentration in an adjacent bulk phase ( liquid or gas ) at a fixed
temperature. In this experiment the applicability of the Langmuir and Freundlich
isotherm will be tested.

Langmuir Isotherm:

If (i) the adsorption is limited to a monomolecular layer, (ii) all sites on the surface
are assumed identical, and (iii) no interactions exist between adsorbed molecules, the
Langmuir isotherm, which is derived next, is often applicable. The derivation is
general although it is outlined below for our system of adsorption of acetic acid from
solution on to a solid charcoal surface.

The fraction of the surface occupied by adsorbed molecules is designated  , then

n
  (1)
n
m

where, n is the number of moles acetic acid adsorbed per gram charcoal at an
equilibrium concentration of c , and nm is the number of moles acetic acid per gram
charcoal required to form a monolayer.

The rate of adsorption is proportional to the fraction of unoccupied sites ( 1- ) and
the concentration c ,
60 Adsorption Isotherms of Acetic Acid

v  k (1   ) c (2)
a 1

The rate of desorption is proportional to the number of occupied sites,

v  k  (3)
d 2

At equilibrium these rates are equal, vd  va , so that

k   k (1   ) c (4)
2 1

from which it follows that

c kc
   (5)
(k 2 k1 )  c 1  k c
where k  k1 / k 2 . Substituting for  from equation (1) and rearranging gives

Ce Ce 1
  (6)
n nm k nm

If the Langmuir isotherm adequately describes the adsorption process, then a plot of
Ce
vs Ce will give a straight line with slope equals to 1/nm .
n

Freundlich Isotherm:

Deviations from the Langmuir adsorption are often observed. This may be because
the surface is not uniform or there may be interactions between adsorbed molecules,
or there may be adsorption in more than one layer, that is, multilayer adsorption.
When such deviations occur, the results can sometimes be fitted to the empirical
adsorption due to Freundlich.

x 1/ 
n    Ce . (7)
m

x is the number of moles acetic acid, adsorbed on m gram activated charcoal thus n
is the number of moles of acetic acid adsorbed per gram charcoal. Ce is the
equilibrium concentration of acetic acid in mol/L;  and  are constants for the
system under study.
 Adsorption Isotherms of Acetic Acid 61

By taking logarithm of Eq. (7), we obtain

1
log n  log C e  log  (8)

If Freundlich isotherm is applicable, a plot of log n versus log Ce would give a
straight line with slope equal to 1/ and an intercept equal to log.

Experimental Procedure:

1. Prepare in 100 mL volumetric flasks six solutions of acetic acid (Ci) with
approximate concentrations of, 0.5 M, 0.3 M, 0.2 M, 0.15 M, 0.1 M, and 0.05 M,
all by suitable dilution from 1 M stock solution.

2. Weigh accurately six batches of about 2g of charcoal (m) and place them in each
of six previously cleaned and dried 100mL conical flasks. To each flask add
precisely 50.00 mL (V) of the six acetic acid solutions prepared earlier. Stopper
the flasks tightly and shake for 30 minutes in a shaker.

3. While the samples are being shaken, determine the precise concentrations of the
six acetic acid solutions by titration against a standard NaOH solution, using
phenolphthalein as the indicator. Use 5.00 mL (15.00 mL in the case of the 0.05
M solution) of the acid solution for the titrations.

4. After 30 minutes of shaking, filter the samples through fine filter paper. Discard
the first 10 mL of the filtrate as a precaution against adsorption of acid by the
filter paper.

5. Titrate a volume of 5.00 mL (15.00 mL in the case of the 0.05 M acid) with
standard NaOH using phenophthalein. Determine the equilibrium concentration of
each of the six solutions (Ce)
62 Adsorption Isotherms of Acetic Acid

REPORT:

1. Construct the following table from weighings and titration results:

RUN Ci Ce C x m n

1
2
etc.

where, Ci, is the initial concentration of acetic acid before adsorption in mol/L.

Ce, is the equilibrium concentration of the acetic acid filtrate after

adsorption in mol/L.

C, is the concentration of the acetic acid adsorbed on the surface of the
charcoal
and
C = Ci - Ce in mol/L (9)

From C (mol/L) and the volume V (0.0500 L) the number of moles of acetic acid
(x) adsorbed may be calculated and in turn n can be obtained.

x = C*V and n = x/m

2. Test the applicability of Langmuir and Freundlich isotherms for the acetic
acid/charcoal system using suitable graphs. Obtain the relevant constants from the
slopes and intercepts.

3. Calculate specific area A (in m2/g) for the charcoal sample from:

A  nm L  (12)

where, L is Avogadro's number and  is the area in m2 occupied by the

adsorbed molecule. For acetic acid,  = 21 x 10-20 m2 OR 2.1 x 10-19 m2 .

Reference:

"PHYWE, University Laboratory Experiments CHEMISTRY", Page 1.2.1.10.

 63

DETERMINATION OF SURFACE TENSION

BY THE RING (DU NOUY) METHOD

Objectives:

1. To measure the surface tension () for ethylene glycol and glycerol.

2. To determine the Temperature coefficient k.

3. To determine the total Surface energy per unit area UA.

Theory:

Intermolecular forces in the liquid phase are very much larger than intermolecular
forces in the gaseous phase. As a result the liquid molecules at a gas-liquid interface
experience a net force that points into the liquid phase. The specific surface energy, 
of the liquid is given by:

 = E / A (1)

where, E is the work done to increase the liquid surface area by A, and  is
identical to the liquid surface tension coefficient , given by:

 = F/l (2)

where F is the force acting at the edge of length l tangentially to the surface in order to
maintain the liquid film. Since in this experiment the force is perpendicular to the
perimeter of a ring surrounded by liquid inside and outside the ring then the length is
given as:

l=2x(2r) (3)

where r is the radius of the ring. From equations (2) and (3) we get:

 = F / 4 r (4)

The surface tension  varies with the temperature according to the relationship:
64 Surface Tension by Ring Method

 =  ( Tk - T ) (5)

Where T'k is a temperature close to the critical temperature Tc ; thus, the surface
tension vanishes as the critical temperature is reached. Defining a molar surface
tension, m by:

23
 m   Vm (6)

where Vm is the molar volume of the liquid. From equation (5) into (6) for 

2 3 ( T   T)  k (T   T)
 m   Vm (7)

k k

2 3
where the term  V is called the temperature coefficient k which has nearly
m
constant value of 2.1 x10-7 JK-1 for liquids that do not associate or dissociate. Lower
or higher k values are obtained respectively for liquids that associate or dissociate.

The total surface energy per unit area, UA ,of a liquid film is given by:

UA =  - T( d/dT ) (8)

Where  is the free surface energy or work done for a unit increase in the surface area
and T (d/dT) = TdS = q is the heat absorbed in the process. Note (d/dT) =  = dS
are the change in surface entropy.

Experimental Procedure:

1. Place the liquid (ethylene glycol or glycerol) whose surface tension is to be

measured in a container. This container and therefore the level of the liquid
in it may be raised or lowered by means of a jack.

2. Clean the measuring ring with ethanol, rinse it thoroughly with distilled
water then dry it using a hot air gun. Using the thread provided hang it from
the left-hand arm of the torsion dynamometer. Immerse the ring about 2- 3
mm below the surface of the liquid under study. Set the dynamometer
pointer to 'O' by turning it counter clockwise. To compensate for the weight
of the measuring ring turn the rear knob of the dynamometer until the lever
arm is in the white space between the display markings. Slowly turn the
front knob of the dynamometer clockwise; it will try to pull the ring out of
 Surface Tension by Ring Method 65

the liquid. Continue this process and stop as soon as the distended film at the
surface of the liquid breaks.

3. Read the value of the force F in mN from the dynamometer scale and record
the temperature of the liquid. Given the radius of the ring r equations (2) and
(3) will lead to the surface tension  of the liquid under study at the
experimental temperature.
4. Heat the liquid with continuous stirring up to 105 C approximately. Now
stop heating and measure surface tension at this temperature.
5. Let cool down the liquid and measure the surface tension at an interval of
10 to 15 C for 5 measurements up to room temperature.

DYNAMOMETER
REPORT:

1. Provide the data of F as a function of T for both liquids in the form of a

table.

2. Using equation (4) calculate the surface tension values  at all the
temperatures studied for both liquids and make a plot of  versus T.

3. From linear least squares fits of  vs T find the slope (d/dT) and calculate
UA and k for both liquids at 25 C. (Note that although the total surface
energy per unit area, UA, can be calculated from the intercept, it is supposed
66 Surface Tension by Ring Method

to be a function of temperature. The reason for it to appear more or less

constant is because UA is varying very slowly in the temperature range we
are studying.)

4. Discuss your k values and compare them with the nearly constant value of
2.1x10-7 JK-1 for liquids that do not associate or dissociate.

5. Compare, for each of the liquids studied, the value of lit at a certain
temperature with exp obtained from linear regression.

Reference:

"PHYWE, University Laboratory Experiments CHEMISTRY" , p. 3.2.4.

 67

LIQUID VISCOSITY

1. FALLING BALL METHOD:

Objectives:

1. To determine the viscosity of glycerol.

2. To determine the activation energy of the viscous flow.

Theory:

The frictional resistance F for a spherical ball of radius r falling at velocity v through
a liquid of viscosity  is given by

F  6  r v (1)

The gravitational force F' on the ball is equal to its effective mass times the
acceleration of gravity g; the effective mass is the mass of the sphere minus the mass
of the displaced liquid. Then if  is the density of the sphere and 0 is the density of
the liquid,

F   4  r 3 ( - 0) g (2)
3

When the ball is falling at a constant velocity,F = F', and (1) and (2) give

2 g r 2 (   o )
  (3)
9v

If the liquid is in a cylinder of radius R, a correction must be applied for the effect of
the container walls on the motion of the liquid as the ball falls, giving

 2 gr 2 (  o )   r  r 
3

   1  2.104    2.09    ... (4)
9v R  R 
   

This method is suitable for measurements on liquids of high viscosity, in the range
10 to 10000 poise.
68 Liquid Viscosity

For most liquids the dependence of viscosity () on temperature T may be written

  A exp ( Ea / R T ) (5)

where R is the gas constant, A is a constant, T is the temperature in Kelvin and E a is

the activation energy for viscous flow.

In this experiment the falling ball method is used to determine the viscosity of 1,2,3-
propanetriol (also called glycerine or glycerol) as a function of temperature, and the
activation energy for viscous flow is found.

Experimental Procedure:

1. Three cylinders filled with glycerine thermostated (at about 0C, 15C, 25C) by
circulation of water through their jackets are available for use in the falling ball
method. To allow the glycerine to reach the temperature of the bath, wait at least
1 hour.
2. Three sizes of cleaned and well-dried stainless steel balls, having diameters 3/32,
1/8 and 5/32 inches, are used in the experiment. Find the density of the steel balls
from the Handbook.
3. With a clean, dry thermometer, measure the temperature of the glycerine in the
cylinders. Measure the time needed for the smallest balls to fall 200 mm (using
the marked lines on the containers) at each temperature. Repeat each measurement
two times.
4. Repeat step 3 at at 0°C for the larger balls.

REPORT:
1. Using the average time for each trial, determine the values of  using equation (4).
Tabulate and discuss the results for the different sizes of balls at 0°C.

2. Using equation (5) determine Ea of glycerine by plotting ln  vs. 1/T.

3. Compare the results for  from your experiment with the values of  from the
literature. Interpolate by linear regression the temperature used in the experiment.

4. Compare the Ea obtained from experiment with the literature value which can be
obtained by fitting the literature data to equation (5).
 Liquid Viscosity 69

Fig l: FALLING BALL METHOD:

Cylinder Containing Glycerine

Fig II: OSTWALD VISCOMETER

OSTWALD VISCOMETER
70 Liquid Viscosity

Part II: OSTWALD VISCOMETER

Objectives:

1. To determine the viscosities of a series of normal alkanes and primary

alcohols.

2. To compare the precision and accuracy of measuring viscosities using the

falling ball method of measuring viscosities with that using the Ostwald
viscometer.

Theory:

Another method for determining viscosities is to measure the time for a fixed volume
of liquid to flow through a capillary tube. Such viscometers are manufactured with a
wide range of capillary diameters; it is necessary to choose the size appropriate to the
viscosity of the liquid being studied, so that it will take a few minutes for the liquid to
drain through the tube. This type of viscometer can be used for liquids of viscosity up
to 100 poise.

Analysis of the flow of liquid of density  and viscosity  through an Ostwald

viscometer gives

(6)
where t is the time needed for the liquid to flow between the two marks on the
viscometer, and A is a constant depending on the viscometer. A is found from
measurements using a liquid of known viscosity to calibrate the viscometer. Water is
used for this purpose in this experiment. Then a series of linear alkanes and a series
of primary alcohols will be studied, and their viscosities will be determined.

Experimental Procedure:

1. For each liquid studied, the procedure is the same. In order to obtain accurate,
reproducible results, the viscometer must be very clean. For each new liquid
studied, rinse the viscometer by using an aspirator with a water trap to suck the
liquid through the viscometer.

2. Put 4.00 ml of the liquid in the viscometer and clamp it in the water bath,
which should be set to 20 C.
 Liquid Viscosity 71

3. Allow at least 15 minutes for temperature equilibration, and record the

temperature of the bath.

4. Using a pipet filler, suck the liquid to above the upper mark on the viscometer,
and then measure the time needed for the liquid to drain between the two marks.

5. Repeat the measurement; the results should agree to within 0.3 seconds. If not, or
if liquid drops are sticking in the viscometer,
it should be cleaned again and the experiment repeated.

REPORT:

1. From the reference, find the viscosity and density of water at the bath temperature.
Use these values in equation (6), with the experimental results for water, to find
A. Look up the densities of the liquids studied, at the experimental temperature.

2. Use equation (6), to determine the viscosities of these liquids.

3. Compare the results to the literature values from the reference.

4. Discuss the trends found for the series of alkanes and for the series of alcohols,
and discuss the difference in viscosity between the alkanes and the alcohols.

Reference:

"Handbook of Chemistry and Physics," 70th ed., pages, F4-5, C42-553, F41-46, F40.
CRC Press, Boca Raton, Florida (1989-90)
 73

GAS VISCOSITY

Objectives:

1. To determine the viscosities of dry Air, CO2 and He gases.

2. To determine the molecular diameters of the gases to be studied.

Theory:

When one layer of fluid (liquid or gas) flows past another, friction between the layers
slows down the faster layer and speeds up the slower one. A force F must then be
applied to maintain the velocity gradient (dv/dx) between the layers. If A is the area of
each layer,

F   A dv (1)
dx

where  is called the coefficient of viscosity or simply the viscosity: it is a measure of

the friction between the layers.  has the units Kg m-1 s-1 . Equation (1) is called
Newton's law of viscosity.

In the case of gases, equation (1) can be derived from the kinetic molecular theory.
Molecules of the gas can move between the layers, and collisions between molecules
then tend to make the velocities of the layers equal. It can be shown that, for an ideal
gas,

(RTM ) 1/ 2  25 (RTM )
1/ 2
  2 .96  10 (2)
(N  3/ 2  2 ) 2

where M is the molar mass and  is the molecular diameter of the gas molecule.
It should be noted again that the numerical coefficient above has units of mole .

In the case of a gas flowing through a capillary of radius r and length l, the volume V
of gas flowing under pressure P through the capillary in time t can be shown from
equation (1) to be

 Pr4 t
V 
8l

 Pr4 t
thus,  (3)
8V l
74

This is known as the Poiseuille equation. Direct application of equation (3) requires
the flow to take place under constant pressure. However, it is easier experimentally to
measure the pressure change as a certain volume of gas flows through a capillary.
This can be done using the apparatus shown in the figure. A gas in the bulb is
evacuated through the capillary and the pressure is measured as a function of time. In
this case the Poiseuille equation gives

1  1  r t
4
(4)
P Po 16  lV

where Po is the initial pressure at t = o and V is the volume of the system. When the
same apparatus is used to take measurements on several gases, the apparatus
dimensions are constant, and combining all constants gives

1  1  ct (5)
P Po 

A plot of 1/P versus t then gives a straight line with slope c/

Experimental Procedure:

1. At the beginning of the experiment, and each time a new gas is to be studied,
the system must be purged completely. To do this, evacuate the system, then
fill it with the gas of interest and evacuate again. Do this at least twice. Be
sure to pump some of the gas through the capillary tube each time.

2. Fill the system with the gas to be studied to about atmospheric pressure. If
the gas is laboratory air, dry it by passing it through a drying agent. Record
the original pressure (time t=0) and the room temperature.
3. Open the two-way stopcock so that the gas is being pumped through the
capillary tube, and start the clock at the same time.

4. Record the time for every 60 mm Hg pressure change; continue until 8 to 10

readings are taken. Close the stopcock.

5. Repeat steps 1 to 4 for the other gases studied.

 75

Figure 1: The gas viscosity setup

REPORT:

1. Show in a table your experimental values of P and 1/P as a function of time

for each gas at the experimental temperature.

2. Plot 1/P versus t for each gas, and determine the slopes of the resulting
(straight) lines.

3. From equation (5) the slope is given by c/ so that  cannot be determined
unless c, which depends on the dimensions of the apparatus, is known. This
problem is avoided by using dry air as a reference gas. Numerous
measurements have given the Sutherland expression for the viscosity of dry
air in poise (1 poise = 1x 10-1 Kg m-1 s-1 ) as a function of temperature:

.     T / 
air  (6)
( T  . )

Use this expression to find the viscosity of dry air at the experimental
temperature.

4. Then from equation (4), for two gases a and b,

76

slopea ( c/ a ) b
  (7)
slopeb ( c/b )  a

Use your experimental data for dry air and this expression to find the absolute
viscosities of the other gases studied.

5. Carry out an analysis for units in equation (2) for  which should be in SI
units of Kg m-1 s-1 . What should be the SI units for M in equation (2).
6. Use these viscosities in equation (2) to determine the molecular diameters of
the gases studied.

7. Compare your results to literature values given in reference 4. Discuss your

results.

Reference:

1. Shoemaker, D.P., Garland, C.W., Steinfeld, J.I., and Nibler,

J.W.,"Experiments in Physical Chemistry", 5th Edition, McGraw-Hill, N.Y.,
1989. pages 130-140.

2. Salzberg, H.W., Morrow, J.I., Cohen, S.R., and Green, M.E.,"Physical

Chemistry Laboratory", MacMillan, N.Y., 1978. pages 120-123.

3. Adamson, A.W., "A Textbook of Physical Chemistry", 2nd Edition,

Academic Press, N.Y., 1979. pages 56-59.

4. Moore, W.J.,"Physical Chemistry", 4th Edition, Prentice-Hall, New Jersey,

1972. page 157.
 77

ABSORPTION SPECTRUM OF CONJUGATED DYE

Objective:
To validate the simple particle in a box (PIB) model for  electron
systems of conjugated cyanine dyes.
Theory:

In the UV-Vis Absorption spectrum various

kinds of electronic excitation may occur in
organic molecules as shown on the left. Of
the six transitions outlined, only the two

lowest energy ones (left-most, colored

blue) are achieved by the energies available
in the 200 to 800 nm spectrum. As a rule,
energetically favored electron promotion
will be from the highest occupied
molecular orbital (HOMO) to the lowest
unoccupied molecular orbital (LUMO). In the conjugated hydrocarbons, the
energetically most favorable π __> π* excitation occurs from the highest energy
bonding pi-orbital (HOMO) to the lowest energy antibonding pi-orbital (LUMO).
Increased conjugation brings the HOMO and LUMO orbitals closer together. The
energy (ΔE) required to effect the electron promotion is therefore less, and the
wavelength that provides this energy is increased correspondingly (λ = h • c/ΔE).

In this experiment, three cyanine dyes for which particle-in-a-box (PIB) theory works
well. The structural formulas of these dyes are shown below.

Dye (A) Dye (B)

Dye (C)
Figure 1: Chemical structure of three cyanine dyes, (A) 1,1'-Diethyl-2,2'-cyanine iodide, (B)
1,1'-Diethyl-2,2'-carbocyanine iodide, and (C) 1,1'-Diethyl-2,2'-dicarbocyanine iodide
78

In these molecules, the two nitrogen atoms

represent a substantial disruption of the
conjugated system, so the box length can be
taken as the distance between the two nitrogen
atoms. In this model, a particle of mass m
travels in one dimension (x) box between walls
Figure 2: PIB potential Energy Diagram
separated by L-distance and of potential energy
(V) = 0 has Schrödinger equation at 0 > x >L is:

(1)

where ħ = h/2 and h is Planck's constant. Solution of this equation of a quantum-

mechanical particle exists only for specific stationary states with energies:

(2)

A system of N free electron will have n1 = N/2 highest occupied level, then for the
lowest energy electronic transition between n1 and (n1+1) levels:

(4)

Since E = h = hc/, then the wavelength  of the photon absorbed in this transition
is given by:

(5)

By denoting the number of carbon atoms in the conjugated system by p, then N = p +

3 (one free electron per each carbon + three from the two nitrogen), and the length of
the chain between the nitrogen atoms should be L = (p + 3)lCC, number of bonds in the
chain plus one bond distance on each side multiply with length between atoms lCC
along the chain, this gives:

(6)

Putting lCC = 1.39 x 10-10 m (the bond length in benzene, a molecule with a similar
bonding) and converting  from meter to nanometer (1 m = 109 nm), one get:
 79

(7)

Experimental Section:

1- Instruction for operating the UV-Vis spectrometer will be made available in the
laboratory (also shown in Appendix A), follow the operational outlines, steps 1,2,
and 3, to setup spectrometer.

2- Rinse a cuvette having 1 cm path length thoroughly with Reagent Grade ethanol
solvent then fill it with ethanol, carefully wipe from outside, place it in the
spectrometer compartment, and record baseline from 400 to 800 nm (step 4 in the
Appendix A).

3- Appropriate dye stock solutions (concentration ~ 10-3 M) of three dyes (Dye A, B,

and C) are prepared in ethanol.

4- Choose any one of the available dyes, and obtain its initial spectrum within the
scan range 400-800 nm (Step 5 and 6 in Appendix A).

5- Follow the proposed dilution protocol of the chosen dye (will be provided in the
lab) and re-determine the spectrum using the same cuvette after rinsing and filling
it with the solution under testing (Repeating step 5 and 6 in Appendix A).
Hints:
1- The final diluted solution should have an absorbance ≤ 1 at the peak
maximum.
2- The band shape may change with concentration, since these dyes dimerize.
At the final concentration used, the monomer band (higher wavelength
band) will be much more prominent than the dimer band, which will
disappear or remain as a shoulder on the low wavelength side of the main
peak.
6- Repeat 4 and 5 for the other dyes and obtain
their spectra in the same way (Step 5 and 6
in Appendix A).

7- Copy the data to PC and use the Jenway

Program to locate the long wavelength
maximum (See Figure 3) absorbance and
annotate the peak with max in the spectrum
for each dye.
Figure 3: Dye’s sample spectrum
8- Paste a copy of each spectrum digital data
into an excel sheet and print out copies of the full spectrum for your report.

(Important Safety Note: Conjugated dyes are known sensitizers, wash hands
carefully after using)
80

Report:

1. Display the absorbance curve (A versus ) for each of the final

solution.
2. Determine Amax and max, at the peak of the long wavelength one per
dye.
3. Use Eq. (5), calculate the effective box length L.
4. Use Eq. (7), calculate  from the free-electron model.
5. Use Eqs. (8) and (9), calculate f for each dye, determine whether the
transitions are allowed or forbidden. (Appendix B, Optional)
6. Report your computed values of max using equations 7 and 10 (if
needed) together with the correct box length per each member of the
series.
7. Plot the box length, L, versus the number of the conjugated bonds
forming the box, N, where the regression line fit to the equation L =
l.N + E. The value of l, representing the average bond length, and the
value of E, the effective size of the end group. Compare L-Effective
and L-PIB, if no agreement, use Eq. (8).
8. Choose  to give the best fit for both series and comment on the
nature of polarization (if any). (Appendix B, Optional)
9. Compare experimental results of max and L-values with the PIB-
molecular model values and give the % error, comment on these
results especially estimated box length compare to the L-effective
values.
References:
[1] D.M. Sturmer, in Kirk-Othmer Encyclopedia of Chemical Technology, John
Wiley & Sons, Inc., 2000.
[2] Atkins, P. W. and J. de Paula Physical Chemistry, 10th Edition. New York: W.
H. Freeman, 2014. P.W.
[3] H. Kuhn, J. Chem. Phys., 1949,17, 1198.
[4] Garland, C. W., J. W. Nibler, D. P. Shoemaker Experiments in Physical
Chemistry, 8th Edition. New York: McGraw-Hill, 2009.
[5] J. M. Hollas Modern Spectroscopy, 2nd Edition. New York: Wiley & Sons,
1992.

Appendix A: How can you operate the UV-Vis Spectrometer?

 81

PIB-To Operate Spectrometer

START

Step 2: Step 1
Spectrum Log in
CHEM311
Pin Code
0000

Step 3-Touch and Type

Sec-51

800

Public

Off
G-01
0.0
1.1 On

Step 4:
Place the blank Step 6:
(Solvent) and run
Baseline Press to save the scan
results

Replace with new

Step 5: samples and
repeat steps 5
Replace blank with sample and run Scan for sample
and 6

Appendix B: How do you obtain the oscillator strength? [OPTIONAL]

82

The spectrum details, absorbance and the width of spectrum, and the concentration of
dye molecule can be also used to find the oscillator strength for the lowest energy
electronic transition. The significance of the oscillator strength comes from the fact that
the value for f is different for allowed and forbidden transitions. For an allowed electronic
transition f  1, while for a forbidden electronic transition f is typically around 10-3. The
oscillator strength, f, is defined as

(8)

where 0 is the permittivity of free space, me is the mass of the electron, c is the speed
of light, e is the electron charge, and NA is Avogadro’s number.

The integral in Eq. (8) is in terms of frequency and is derived from Einstein’s model
for light absorption and emission to give:

(9)

where , Amax is the experimental

absorbance of the dye at the peak of the spectrum,
C is the concentration of dye molecule in solution
(in units of mol/L) and lis the path length of the
cuvette (1.00 cm for a standard cuvette). is the
width of spectrum (in units of cm-1) and can be
Figure 3: Dye’s sample spectrum
found by converting the wavelengths
corresponding to the base of the triangle used to approximate the absorption band as a
triangle, as shown in the example in Figure 3. Since the base of the triangle runs from
715. nm (13990. cm-1) to 810. nm (12350. cm-1), then  = (13990. – 12350.) = 1640. cm-1.

Note: If there are easily polarizable groups at the ends of the chain, the potential
energy of the  electrons in the chain doesn’t rise so sharply and then the L is
modified to L = (p + 3 + )lCC, where  should lie between 0 and 1, to give:
 83

FLUORESCENCE QUENCHING OF
RHODAMINE B DYE

Objective:

To utilize the absorption and fluorescence spectroscopy of rhodamine-B

dye to determine its fluorescence quenching process with aliphatic
amines.

Theory:

When molecule is electronically excited by the absorption of a photon,

there are a number of schemes by which it can then return to the ground
state. One mode involves the emission of a photon of light, which causes
the substance to fluoresce. Alternatively, species can lose their excitation
by nonradiative schemes such as dynamic quenching. Fluorescence
lifetime measurements are often used to investigate the various modes of
de-excitation that occur following photo-excitation.

The following reactions represent the deactivation of a temporary

generated excited state molecules [A*]:

1. A* can return to the ground state by simple fluorescence,

(1)

2. and by non-radiative decay

(2)

where k1 and k2 are the rate constants for these two processes. With only
these two paths to the ground state available, the rate equation for [A*]
can be written as
84

(3)

Rearrangement and integration of equation (3) with respect to initial

conditions between t = 0 at which and [A*] = [A*]0 gives,

(4)

Thus, the ‘fluorescence lifetime in the absence of quencher’ is given by

(5)

τ0 is the amount of time that it takes for the fluorescence intensity to

decay to 1/e its initial value.

A typical fluorescence decay

curve is shown in Figure 1 (the
time axis is in units of
nanoseconds). The fluorescence
intensity spikes upward when
the sample is irradiated by the
Figure 1: Typical fluorescence decay curve
light pulse (at 10 ns), and the
intensity decays away in an exponential fashion (the lifetime associated
with this particular curve is approximately 30 ns).

In the presence of a quenching agent (Q) in solution, the mechanism of

the interaction between quenchers and macromolecules could be static or
dynamic quenching [1]. Static quenching refers to the formation of a non-
fluorescence fluorophore – quenching complex. Dynamic (Collisional)
quenching refers to the quencher diffusing towards the fluorophore
during the lifetime of the excited state and, upon contact, the fluorophore
 85

returns to the ground state without emission of a photon. Thus, an

additional process should be included in the deactivation of the excited
molecules:

returning A* molecules to the ground state by the effect of a quenching

agent;

(6)

and the rate equation for [A*] will be modified to

(7)

kq which appears in equations (6) and (7) is called the bimolecular

quenching constant. Assuming [Q]>>[A*], which can be treated as a
constant, thus equation (7) can be integrated to give

(8)

Consequently, the fluorescence decay is still exponential, but the

fluorescence lifetime (with quencher) becomes

(9)

Dividing equation (9) into equation (5) gives

(10a)

or

(10b)
86

According to equation (10b), a plot of τ0/τ versus [Q] should be linear

with an intercept equal to one, and the slope can be analyzed to obtain the
bimolecular quenching rate constant, kq. Such a plot is called a Stern-
Volmer plot. The quenching rate constant value is used to distinguish the
dynamic and static type of quenching process. According to the literature
[2,3] for dynamic quenching, the maximum scatter collision quenching
constant of various quenchers with the biopolymer is 2.0 x 1010 L mol-1 s-
1
and their fluorescence lifetime is 10-8 S.

In this experiment, the analysis of fluorescent lifetime of Rhodamine-B

(RhB) in presence of aliphatic amine, triethyl amine (TEA) [4], will be
used to determine kq. The used amine will interact with RhB base and
quench its intrinsic fluorescence. The predicted value of kq will be used to
identify which type of quenching, dynamic or static, is quenching process
or RhB with amine.

In the case of the static quenching, the absorbance (A) or emission (F)
intensities can be utilized to obtain the ground or the excited states
equilibrium processes using the variation in their intensities as function of
the quencher concentrations as follows:

(11)

Using the equilibrium constant and hence the standard Gibb’s energy it is
possible to estimate which off the absorbance or emission process is
spontaneous.
 87

Experimental Section:

1. Prepare solutions of 2.0 x 10-4 mol L-1 RhB and 2.0 x 10-4 mol L-1
TEA in 5% methanol.

2. Several mixtures of RhB/TEA in 5% methanol are prepared as

indicated in the following Table 1 into a 10 mL volumetric flask and
then mixing fully.

Table 1: Aliquots of RhB and TEA for different runs

RUN RhB TEA 5% Methanol
1 5.00 mL - 5.00 mL
2 5.00 mL 1.00 mL 4.00 mL
3 5.00 mL 2.00 mL 3.00 mL
4 5.00 mL 3.00 mL 2.00 mL
5 5.00 mL 4.00 mL 1.00 mL
6 5.00 mL 5.00 mL -

3. For each run, clean and rinse a 1 x 1 cm fluorescence transparent

quartz cuvette.

4. Fill the mixture into the cuvette, wipe off the finger prints from four
sides, and place it in the sample chamber of the testing spectrometer.

5. For the absorbance measurements, an absorption scan within the range

of 450-600 nm is recorded for each solution and the absorbance
intensity (A-value) at the (abs)max of each solution is reported.

6. For the emission measurements, a full fluorescence emission spectrum

is recorded in the range of 500-650 nm is recorded for each solution
and the fluorescence intensity (F-value) at the (emi)max each solution
is reported.

7. Fluorescence decay curves of each solution obtained and then

analyzed after using the proper chatterer (drop of milk in 5 mL
distilled water) to reported the time resolved decay of each solution
88

Report:
1. Figure 1 of overplayed absorption spectra of pure Rhodamine B base
solution and its complex with TEA from the different run

2. Figure 2 of overplayed Fluorescence emission spectra of pure

Rhodamine B base solution and its complex with TEA from the
different run

3. Figure 3 of overplayed decay curves of pure Rhodamine B base

solution and its complex with TEA from the different run

4. Table 2 of the experimental peak intensities and life time of the decay
curves

Table 2: Absorbance intensity, Fluorescence intensity, and life

time of the decay curves of RhB and RhB/TEA complex
RUN [RhB]/M [TEA]/M A (a.u.) F (a.u.) ns
1 1 x 10-4 0.0

2 1 x 10-4 2 x 10-5

3 1 x 10-4 4 x 10-5

4 1 x 10-4 6 x 10-5

5 1 x 10-4 8 x 10-5

6 1 x 10-4 1.0 x 10-4

5. Enter each data set into an excel sheet and generate Stern-Volmer
plots for each (i.e. plot the data according to equation (10b) and
include a best-fit line) and answer the following questions:
a) Is the data linear?
b) Does the intercept equal 1 as predicted by this model?
c) Calculate the bimolecular quenching rate constant (kq).
d) Is the quenching process dynamic and static type?
 89

e) Estimate the equilibrium constants of the ground state complex, Kg,

and the excited state one, Ke, from the plots of [A0]/[A] vs. [Q] and
[F0]/[F] vs [Q].
f) What will be the free energies, Gg and Ge, of these complexes
formation using the Gibbs’ relation G = -RT ln K?
6. Theories developed by the British physicist George Stokes and Albert
Einstein on the topic of diffusion can be combined to obtain the
Stokes-Einstein equation

(12)
which is useful for approximating the rate constant for diffusion
limited bimolecular collisions (kd) in solution. In this equation, R is
the universal gas constant, T is absolute temperature, and η is the
viscosity of the solvent. Water is the solvent employed in the
fluorescence lifetime experiments presented here; the viscosity of 5%
methanol-water is η = 1.100 cP (centipoise) at 298 K [NOTE: 1 Poise
= 0.1 kg/(m s)].

Use the Stokes-Einstein equation to calculate the diffusion limited

bimolecular rate constant in water and compare the value you obtain
to the bimolecular quenching constants (kq) determined from the last
plot. Based on your comparison, what fraction of the collisions
between the fluorophore and the quencher are 'effective' in actually
quenching the fluorescence?
Reference:
1. L.K. Fraiji, D.M. Hayes, and T.C. Werner, Static and dynamic fluorescence
quenching experiments for the physical chemistry laboratoryJournal of Chemical
Education, 69(5), 424 (1992).
2. H. Cao, D. Wu, H. Wang, M. Xu, Effect of the glycosylation of flavonoids on
interaction with protein, Spectrochim. Acta A 73 (2009) 972–975.
3. T.G. Dewey, Biophysical and Biochemical Aspects of Fluorescence Spectroscopy,
Plenum Press, New York, 1991. 1–41.
4. S. Bakkialakshmia, P. Selvaranib, S. Chenthamaraic. Fluorescence quenching of
Rhodamine B base by two amines. Spectrochimica Acta Part A: Molecular and
Biomolecular Spectroscopy, 105, 557 (2013).
http://dx.doi.org/10.1016/j.saa.2012.11.091
90

VIBRATIONAL-ROTATIONAL SPECTRA
OF HCL AND DCL

Objective:

To utilize pure rotational-vibrational transitions in gas-state HCl and DCl

to determine force constant, isotope effect, and equilibrium bond length.

Introduction:

The infrared region of the spectrum extends from the long-wavelength

end of the visible region at 1 µm out to the microwave region at about
1000 µm. It is common practice to specify infrared frequencies in
wavenumber units: ṽ (cm-1) = 1/λ = v/c, where c is the speed of light in
cm.s-1 units. Thus, this region extends from 10,000 cm-1 down to 10 cm-1.
Although considerable work is now being done in the far-infrared region
below 400 cm-1, the spectral range from 4000 to 400 cm-1 has received the
greatest attention because the vibrational frequencies of most molecules
lie in this region. In this experiment, FTIR spectroscopy was used to
analyze rotational-vibrational transitions in gas-state HCl and DCl and
their isotopomers (due to 35Cl and 37Cl) to determine molecular
characteristics.

Theory, Almost all-infrared work makes use of absorption techniques in

which radiation from a source emitting all infrared frequencies is passed
through a sample of the material to be studied. When the frequency of
this radiation is the same as a vibrational frequency of the molecule, the
molecule may be vibrationally excited; this results in loss of energy from
the radiation and gives rise to an absorption band. With sufficiently high
resolving power, a vibration spectrum can be obtained that not only
shows the vibration excitation, but also the rotation excitation within it.
Figure 1 depicts this overlay of both rotational and vibrational energies:
 91

Fig. 1 – Rotational levels, J, superimposed the vibrational

levels, v, and the P & R branches

This change in vibrational energy (ν = 0 to ν = 1) with several different

rotational energy changes (J = ±1) leads to the splitting in a typical
rotational-vibrational spectrum shown in Figure 2.

Fig. 2 – HCl Full FTIR Spectrum.

The simplest model of a vibrating diatomic molecule is a harmonic

oscillator, for which the potential energy depends quadratically on the
change in internuclear distance. The allowed energy levels of a harmonic
oscillator, as calculated from quantum mechanics is

(1)
92

where v is the vibrational quantum number having integral values 0, 1, 2,

... ; v is the vibrational frequency; and h is the Planck constant.

The simplest model of a rotating diatomic molecule is a rigid rotor or

"dumbbell" model in which the two atoms of mass m1 and m2 are
considered to be joined by a rigid, weightless rod. The allowed energy
levels for a rigid rotor may be shown by quantum mechanics' to be

(2)

where the rotational quantum number J may take integral values 0, 1, 2,

.... The quantity I is the moment of inertia, which is related to the
internuclear distance r and the reduced mass and are given by

by I = µr2 and µ = (3)

Since a real molecule is undergoing both rotation and vibration

simultaneously, a first approximation to its energy levels E(v , J) would
be the sum of expressions (1) and (2). A more complete expression for
the energy levels of a diatomic molecule is given below, with the levels
expressed as term values T in cm-1 units rather than as energy values E in
joules:

(4)

where c is the speed of light in m s-l, e is the frequency in cm-l for the
molecule vibrating about its equilibrium internuclear separation re, and

(5)
 93

The first and third terms on the right-hand side of Eq. (4) are the
harmonic-oscillator and rigid-rotor terms with r equal re. The second term
(involving the constant xe) takes into account the effect of anharmonicity.
Since the real potential u(r) for a molecule differs from a harmonic
potential, the real vibrational levels are not quite those given by Eq. (1)
and a correction term is required. The fourth term (involving the constant
De) takes into account the effect of centrifugal stretching. Since a
chemical bond is not truly rigid but more like a stiff spring, it stretches
somewhat when the molecule rotates. Such an effect is important only for
high I values, since the constant De is usually very small. The last term in
Eq. (4) accounts for interaction between vibration and rotation. During a
vibration, the internuclear distance r changes; this changes the moment of
inertia and affects the rotation of the molecule. The constant αe is also
quite small, but this term should not be neglected.

Selection Rules, The harmonic-oscillator, rigid-rotor selection rules are

Δv = ±1 and ΔJ = ± 1; that is, infrared emission or absorption can occur
only when these "allowed" transitions take place. For an anharmonic
diatomic molecule, the ΔJ = ± 1 selection rule is still valid, but weak
transitions corresponding to Δv = ±2, ±3, etc. (overtones) can now be
observed.'

Since we are interested in the most intense absorption band (the

“fundamentalˮ), we are concerned with transitions from various J' levels
of the vibrational ground state (v = 0) to J" levels in the first excited
vibrational state (v"). From the selection rule we know that the transition
must be from J' to J" when J = +1 ( J' = J" + 1) and J = -1 ( J' = J" - 1)
to produce frequency ṽ (in wavenumbers) for this transition will be just
T(v', J') - T(v", I") as follows:

(6)
(7)

where the De term has been dropped and ve, the frequency of the
forbidden transition from

(8)
94

The two series of lines given in Eqs, (6) and (7) are called R and P
branches, respectively. These allowed transitions are indicated on the
energy-level diagram given in Fig. 1. If e were negligible, Eqs. (6) and
(7) would predict a series of equally spaced lines with separation 2Be
except for a missing line at ve. The effect of interaction between rotation
and vibration (nonzero e) is to draw the lines in the R branch closer
together and spread the lines in the P branch farther apart as shown for a
typical spectrum in Fig. 3.

Fig. 3 – Rotational transitions of P & R branches with isotope effect

For convenience let us introduce a new quantity m, where m = J" + 1 for

the R branch and m = -J" for the P branch as shown in Fig, 3, It is now
possible to replace Eqs. (6) and (7) by a single equation:

or (9)

where m takes all integral values and m = 0 yields the frequency ṽo of the
forbidden "purely vibrational" transition. If one retains the De term of Eq.
(4) (which assumes D" = D' = De)' Eq. (9) takes the form

ṽ (m) = ṽo (m+1) - ṽo (m) = (2Be - 3αe) - 2αe m (10)

 95

A plot of ṽ vs. m can be used to determine Be and αe. Similarly, a

multiple linear regression can be performed to determine ṽo, Be, αe, and
De.

Isotope Effect. When an isotopic substitution is made in a diatomic

molecule, the equilibrium bond length re and the force constant k are
unchanged, since they depend only on the behavior of the bonding
electrons. However, the reduced mass does change, and this will affect
the rotation and vibration of the molecule. In the case of rotation, the
isotope effect can be easily stated. From the definitions of Be and I, we
see that

=
where an asterisk is used to distinguish one isotopic molecule from
another.
For a harmonic oscillator model, the frequency ṽe in wavenumbers is
given by

(11)

which leads to the relation

(12)
96

Experimental:
A general description of infrared instruments is given in Fig. 4. Medium
to high resolution is required for this experiment; a grating or FTIR
instrument with at least 2 cm-1 resolution is desirable. In addition grating
spectrometers require careful calibration. CO and CH4 are suitable gases
for calibration purposes. Detailed instructions for operating the
spectrometer will be given in the laboratory.

Fig. 4: General description of IR-Spectrometer and its results of the

reference (Background)

The infrared gas cell is constructed from a short (usually 10-cm) length of
large-diameter (4 to 5 cm) Pyrex tubing with a vacuum stopcock attached.
Infrared-transparent windows are clamped against O-rings at the ends of
the cell or are sealed on the ends with Glyptal resin. For studies
concentrating on the region 4000 to 700 cm-1, NaCl windows will
suffice. When the spectrum of interest extends down to -400 cm-1 , KBr
windows are needed. Both types of salt windows become "foggy" on
prolonged exposure to a moist atmosphere and should be protected (e.g.,
stored in a desiccator) when not in use. In the present experiment, inert
sapphire windows with transmission down to 1600 cm-1 are particularly
convenient and relatively inexpensive. Filing the cell and Recording the
spectra. An arrangement for filling the cell is given in Fig. 5.
 97

Fig. 5: Arrangement for filling the IR-Cell using vacuum manifold

The manifold is relatively straightforward in use. Numbers 1-5 are

stopcocks. The pump trap was a trap that a thermos filled with liquid
nitrogen surrounded to condense any gas-phase HCl before it reached the
vacuum pump. After closing all
stopcocks, the pump was turned on, and stopcock one was opened to
pump the system down in pressure to 1 torr. Stopcock 1 was closed, and
the pressure slowly rose, indicating a leak. This was found to be at the
junction from the gas generator to stopcock 5. This was repeatedly
checked throughout the experiment to ensure proper sealing of the
system. Once the leak was fixed, the system pumped, and the reading
stayed steady at 1 torr, stopcocks 3 and 4 were opened to pump out the IR
gas cell. Once this also reached 1 torr, stopcocks 3 and 4 were closed, and
it was removed and used to create a background spectrum in the FTIR
instrument. This background FTIR spectrum was collected at both 16 cm-
1 and 1 cm-1 resolution. The IR cell was reconnected to the manifold,
and the rest of the experiment began.
The main part of the experiment was divided into two halves – first, the
production of HCl and the associated FTIR analysis, and then the
production of DCl and its associated FTIR analysis.
98

Once the IR cell was reconnected, the first half the experiment began. ~1
gram of NaCl was added to the gas generator cell, and connected to the
manifold. Stopcock 5 was slowly opened to pump out the round-
bottomed-flask (RBF), after which stopcocks 3 and 4 were opened. Once
the entire system was at 1 torr, and stopcock 1 was closed to check for
leaks and a consistent vacuum was achieved, ~1 mL of H2SO4 was added
through a septum on the RBF containing the sodium chloride. This
reaction produced the HCl gas that flowed into the IR cell. Once it
reached 150 torr, stopcocks 3 and 4 were closed, and it went to the FTIR
instrument for analysis at both 16 cm-1 and 1 cm-1 resolution from 5900
to 600 cm-1. As this was being analyzed, stopcock 1 was slowly opened to
pump out the HCl gas, the IR cell was reattached following analysis, it
was also pumped out, and the RBF was removed and cleaned. This was
repeated at an HCl pressure of 100 torr and 207 torr. Once it was
determined that ~100 tor and a resolution of 1 cm-1 were the best
parameters for analysis, the process was repeated but only at 100 torr and
1 cm-1 resolution with deuterated sulfuric acid, D2SO4, for the production
of DCl.

Data and Report:

1- Select your best HCl and DCl spectra, and index the lines with the
appropriate m values as shown in Fig. 6.

Fig. 6: Assignments of the m-values based on J-values

 99

2- Make a table of these m values and the corresponding frequencies

ṽ(m). Express the frequencies in cm-1 units to tenths of a cm-1! if
possible.
3- List the differences between adjacent lines Δṽ(m), which will be
roughly 2Be but should vary with m.
4- Plot Δṽ (m) against m, draw a straight line through the points with
linear regression analysis to fit Eq. (10).
5- Then carry out a multiple linear least-squares fit to the data with
Eq. (9) to determine Δṽ0, Be and αe, and their standard errors.
6- Repeat this fitting procedure using Eq. (10), of both noting that
high m transitions will be the most important ones in determining
De due to its m3 dependence.
7- If 35Cl/37Cl splitting is seen, index the stronger 35Cl lines.
8- Use your values of ṽ0 for HCl and DCl to determine ṽe and ṽe* for
HCl and DCl. From ṽe, calculate k for HCl using equations (11)
and (12).
9- Calculate Ie the moment of inertia, and re the internuclear distance,
for both HCl and DCl. The masses '(in atomic mass units) are H =
1.007825, D = 2.014102, 35Cl = 34.968853, and 37Cl =
36.965903.
10- Tabulate all of your results, along with your estimates of the
experimental uncertainty.
11- Compare your results with literature values.

Discussion:

 Compute the ratio /Be and compare with the rigid-rotor

prediction of. Eq. (11). How constant is re for HCI and DCl?

 Compute Bv = Be - αe (v + ) for the v = 0, 1, and 2 levels of HCl

and DCl and from these obtain average rv values for these levels.
Comment in your report on the changes in these distances.
100

 Compare your / ratio with the ratio (µ/ )1/2 expected for a
harmonic oscillator. How anharmonic is the HCl molecule: i.e.,
how large is xe? Use your values of ṽe and ṽe* and Eq. (4) to predict
the frequencies of the first overtone transitions of HCl and DCl
(ignore the rotational terms).
 Did you see any indication of these overtones in your spectra?
 Do your spectra show any evidence of a 35CI-37Cl isotope effect?
Use Eq. (10) to calculate the splitting expected for this effect for
several P and R branch transitions in HCl and in DCl.

References:

1. P. W. Atkins, Physical Chemistry, 6th ed., chap. 12 and pp. 913-

914, Freeman, New York (1998).
2. G. Herzberg, Molecular Spectra and Molecular Structure I: Spectra
of Diatomic Molecules, 2ded., chap. III, reprint ed., Krieger,
Melbourne, FL (1989); K. P. Huber and G. Herzberg, Molecular
Spectra and Molecular Structure IV: Constants of Diatomic
Molecules, Van Nostrand Reinhold, New York (1979). Although
the latter book is now out of print, its contents are available as part
of the NIST Chemistry WebBook at http://webbook.nist.gov.
3. I. N. Levine, Molecular Spectroscopy, chap. 4, Wiley-Interscience,
New York (1975).
4. I. N. Levine, Physical Chemistry, 5th ed., pp. 846-850, McGraw-
Hill, New York (2002); D. A. McQuarrie, Statistical
Thermodynamics, reprint ed., University Science Books, Sausalito,
CA (1985).
5. G. N. Lewis and M. Randall (revised by K. S. Pitzer and L.
Brewer), Thermodynamics, 2d ed., pp. 60 and 419ff., McGraw-Hill,
New York (1961).
6. H. M. Spencer, Ind. Eng. Chem. 40,2152 (1948).