Physical Chemistry, Year 2, Laboratory Manual Experiment 2

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EXPERIMENT 2

HEAT OF NEUTRALISATION

Background

The heat which is evolved when one mole of an acid is neutralized with one
mole of a base is called the molar heat of neutralization. The object of this
experiment is to measure the molar heats of neutralization of several acids
with the strong base sodium hydroxide.

The experiment is carried out by neutralizing the acid solution with a small
volume of concentrated sodium hydroxide solution. The heat evolved, ∆aH, is
made up of the heat of neutralization, ∆n H, and the heat of dilution of the
sodium hydroxide solution, ∆dH. The heat of dilution of the sodium hydroxide
solution is also to be measured. The heat of neutralization, then, can be
obtained from the equation

∆n H = ∆ a H - ∆d H (A)

Cooling Corrections

Since no adiabatic calorimeter can be insulated perfectly from its

surroundings, there will always be some heat lost from the calorimeter. This
loss of heat can be compensated for.

Heat is generated in the calorimeter either slowly or rapidly. An example of

the former is the heat produced by an electrical heater. The heat produced
when an acid is neutralized with a base is an example of the latter. The
behaviour of the temperature in the calorimeter is shown in Figures 1 and 2,
respectively.
TEMPERATURE, T

ti ( ti + tf ) tf TIME, t

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Physical Chemistry, Year 2, Laboratory Manual Experiment 2
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Figure 1

TEMPERATURE

ti / tf

Figure 2

In Figure 1, the heat produced (uncompensated for heat lost to the

surroundings) is

q = Cp (Tf - Ti) (B)

The times ti and tf are the times at which the heater is switched on and off,
respectively. Ti and Tf are the values of the temperature at those times. To
compensate for the heat lost to the surroundings, ∆T is obtained as shown in
Figure 1. The (corrected) heat produced, then, is

q = Cp ∆T (C)

In Figure 2, since the heat is produced rapidly, ti and tf are taken to be the
same. The uncorrected heat produced is given again by Equation (B), whilst
the corrected heat produced is given by Equation (C).

Experimental procedure

Calibration of the calorimeter

The calorimeter is calibrated electrically with 120 cm 3 of distilled water

(measured with a graduated cylinder), using a current of 0.5A. (see Appendix
A on page 9).

Neutralization of an acid

120 cm3 of 0.5 mol dm-3 HCl solution (measured with a graduated cylinder)
are placed in the calorimeter. After slow stirring, temperature readings are
taken at regular intervals. A graph of temperature vs. time is plotted after each
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Physical Chemistry, Year 2, Laboratory Manual Experiment 2
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reading is taken. When the temperature is changing at a constant rate, 3 cm3

of the concentrated sodium hydroxide solution (100g NaOH in 100g water) is
added, and the time of addition noted. Temperature readings are taken until
the values again change at a constant rate.

The experiment is repeated with each of the following in place of the

hydrochloric acid: nitric acid, acetic acid and monochloroacetic acid.

Heat of dilution of sodium hydroxide

The above procedure is repeated, with 120 cm 3 of distilled water in place of

the acid.

Calculations

The molar heats of neutralization of the various acids are to be calculated.

Discussion

You should account for any similarities and differences in the molar heats of
neutralization of the various acids.

How significant is the loss of heat from the calorimeter to its surroundings?

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Physical Chemistry, Year 2, Laboratory Manual Experiment 2
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APPENDIX A

CALIBRATION OF THE CALORIMETER

In experiments involving heat of neutralization, substances that absorb heat

are water(120 cm3), various types of ions and the calorimeter. Heat capacity
of the system consists of these three parts. Therefore,

Cp = Cp (water) + Cp (ions) + Cp (calorimeter)

Heat capacity is an extensive property i.e. it depends on the mass. Since the
mass of the ions are very small as compared to that of the other substances,
the heat capacity due to the ions can be ignored. So,

Cp = Cp (water) + Cp (calorimeter)

Therefore every single system studied is the same in terms of heat capacity
and the heat capacity of the system has to be obtained.
An experiment to determine the heat capacity of the calorimeter and its
contents is called calorimeter calibration. Calibration is usually carried out
electrically. In this method, the heater (a piece of resistance wire) which is
immersed in water, is switched on and the temperature of the system rises.
From the measurements of temperature rise and the electrical energy used,
the heat capacity of the system can be calculated.
The circuit diagram of an appropriate technique to calibrate a calorimeter is as
shown below.

Let us say the current is I, the potential difference across the

heater,Vp, temperature rise, T and the time the heater is on, t. Therefore,

Cp T = I Vpt
and
Cp = I Vpt/ T
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Physical Chemistry, Year 2, Laboratory Manual Experiment 2
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If no heat is lost to the surrounding,

T = T (heater off) T (heater on).

Otherwise, cooling correction has to be used in order to obtain T.

In general, potential difference can be measured more precisely from the

current. In order to measure the current with the same precision, the ammeter
must be replaced with a piece of standard resistor. If the the potential
difference across the standard resistor is measured, the current can be
calculated by using the Ohm’s law. The new circuit diagram is as follows.

Let say Vr ia the potential difference across the standard resistor R. Therefore

I = Vr/R

Then Cp = Vr Vpt/R∆T

or, Cp/J K-1 = (Vr/V)(Vp/V)(t/s) ⁄ (R/Ω)-1(∆T/K)-1.

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Physical Chemistry, Year 2, Laboratory Manual Experiment5
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EXPERIMENT 5

PARTIAL MOLAR PROPERTIES OF SOLUTIONS

Background

Any extensive property X of a solution can be represented by partial molar properties XA,
XB of the constituent substances A and B, respectively. These molar properties are
functions of the temperature, pressure and concentration of that solution. Here we will take
A as being the solvent while B is the solute. Concerning the volume of a solution, the total
volume, V, is given through the partial molar volume by equation (1)

V = nAVA + nBVB (T, p constant) (1)

where nA and nB are mole fractions.

The partial molar volume can be calculated by measuring the density of the solution.

Apparent molar volume, VB , is defined by equation (2)

VB = ( V - nAVA )/ nB (T, p constant) (2)

where VA is the molar volume for pure A.

From equation (2),

V = nB VB + nAVA (T, p constant) (2a)

and therefore

VB = ( V / nB ) nA ,T , p

= VB + nB( VB/ nB) nA,T, P (3)

and, VA = (V - nBVB)/nA

= [nAVA - nB2( VB/ nB) nA,T,P]/nA (4)

From the density measured from the experiment and the molar mass of both components
MA, MB, VB is given as:

VB = [(nAMA + nBMB)/ - nAVA ]/nB (5)

The molality of the solute is defined by:

mB = nB/(nAMA) (6)

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Substituting nB into equation (5),

VB = ( A - )/(mB A ) + MB / (7)

where A is the density of the pure solvent.

Equation (7) is used to calculate the values of the apparent molar volume from the density
measurements.

Therefore partial molar volumes can be obtained by using equations (3) and (4). You
should plot VB versus nB , but sometimes it is more useful if you plot VB versus mB½.

( VB/ nB) nA,T, P = ( VB/ mB½) nA,T, P ( mB½/ nB) nA,T, P (8)

By using equation (6), equation (8) becomes,

( VB/ nB) nA,T, P = ( VB/ mB½) nA,T, P / (2mB½nAMA) (9)

Therefore VB = VB + ½mB½ ( VB/ mB½) nA,T, P (3a)

and VA = VA* - ½mB3⁄2MA½ ( VB/ mB½) nA,T, P (4a)

Experimental

Prepare accurately an aqueous solution containing about 2, 4, 8, 12 and 16% (w/w) sodium
chloride. For this experiment the total volume required for each solution is 75 cm3. First
determine the volume of the pycnometer by using pure water. Ask the demonstrator about
how to use the pycnometer. Fill the pycnometer with the prepared solutions and determine
their weight. From these measurements determine the respective densities. For each
solution carry out the density determination three times.

Results and Calculation

All weighings must be corrected for air buoyancy (ask the demonstrator). Calculate the
molality of each solution and determine the apparent molar volume VB for each molality.
Plot VB against mB½ and use equations (3a) and (4a) in order to obtain the values of the
partial molar volumes.

Questions

1. How can partial molar volumes indicate the types of interaction between the
components of each solution?

2. What is the significance when you plot VB against mB½ as compared to the plot of
VB against mB for the solutions of sodium chloride in water?

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Note:

(i) Prepare all solutions by accurately weighing the amount of salt and water used
(ii) To make corrections for air buoyancy on all the weights, use the formula below:

Wv = Wa +Wadu (1/dm -1/dw)

Wv = true weight (in vacuum)
Wa = value read from the balance
du = density of air (assumed to be 0.0012g cm3)
dw = 8.0g cm3 (steel density)
dm = density of the weighted object

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Physical Chemistry, Year 2, Laboratory Manual Experiment6
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EXPERIMENT 6

KINETICS OF CHEMICAL REACTION - IODINATION OF

CYCLOHEXANONE

Background

Many reactions that follow simple rate laws actually occur through a series of
steps. These steps are called elementary reactions because they cannot be
broken down further into simpler reactions. The sequence of elementary
reactions that add up to give the overall reaction is called the mechanism of
the reaction.

A mechanism is a hypothesis about the elementary steps through which

chemical change occurs. Sometimes the elementary steps can be studied in
isolation, but in most cases they cannot be easily separated. Sometimes more
than one mechanism could be proposed for a particular chemical reaction,
and evidence of the correct mechanism is often indirect. A valid mechanism
must agree with all the facts about the kinetics and knowledge about the
reactants and intermediates involved. It must be able to explain the rate law
of the backward as well as the forward reaction.

In general, the halogenation of a ketone can be represented as follow:

OR OR
R'-C-C-H +
+ (1)
+ X2 R'-C-C-X H + X
R" R"

where X=halogen atom. This reaction could be catalyzed by H+ in acidic

solution or by OH- in alkaline solution.

Iodination of cyclohexanone

In this experiment, the rate of iodination of cyclohexanone in an aqueous

medium is being measured. To increase the amount of iodine in the solution,
it is necessary to convert to its more soluble complex ion I3- by addition of
excess of iodide ion: I2 + I- I3-.

The overall reaction of iodination of cyclohexanone in an aqueous solution

with excess I- ion can be represented as follows

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Following the rate law of chemical kinetics, the differential rate equation for
the reaction could be written in the following form
-
- d[S] = - d[ I 3 ] = k [S] [I - ] [H+] c
a b
(3)
dt dt 3

where k= rate constant; a, b and c are the orders of reaction with respect to S,
I3- and H+ respectively.

This experiment is carried out to determine the value of k, a, b and c, and to

suggest a mechanism which agrees with the rate equation that has been
obtained.

As the I3- ion is the only colored species in the reaction mixture, a
spectrophotometer could be employed to measure the change in its
concentration, by using the Beer-Lambert Law

A(I3-) = ε l [I3-] (4)

where A = absorbance, = molar absorption coefficient, [ I3-] = concentration

and l = optical path length, that is, the distance traveled by the light through
the solution. The most suitable wavelength for the measurement of I3- ion
concentration is 565 nm.

[Subsequently the absorbance A refers to that due to I3-, measured at 565 nm].

Deriving from equation (4),

-1 -1
[ I-3 ] = l A (5)

where -1 l-1 may be treated as a single constant, and is calculated from the
absorbance measurement made during Spectrophotometer calibration.

The progress of reaction (3) could be monitored by measuring the change in

the concentration of I3- with reaction time.

However, the rate of change in the values of solution absorbance, -dA/dt, can
be correlated to the rate of change in the concentration of I3- by equation (6).

dA -
- d[ I 3 ]
= - l (6)
dt dt

The general rate equation (3) can therefore be written as

dA
k l [S]a [I 3 ]b [H ]c (7)
dt

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Physical Chemistry, Year 2, Laboratory Manual Experiment6
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A direct comparison between rate and concentration can be done

approximately by taking as a measure of the derivative dA/dt the
corresponding ratio of finite increments A/ t.

Then by making a run at each of two different initial concentrations of any one
component, say the cyclohexanone, keeping the other concentrations
constant, the data may be used to determine the order of reaction with
respect to that component.

Let the two rates and corresponding initial concentration be (dA/dt)1, (dA/dt)2,
and [S]1, [S]2, respectively. Then

dA a
k l [I 3 ] b [H ]c [S]1 (8)
dt 1

dA a
k l [I 3 ] b [H ]c [S] 2 (9)
dt 2

From equations (8) and (9), dividing and taking logarithms, we can obtain

dA
log dt 1
dA
a dt 2
(10)
[S]1
log
[S] 2

or a = {log (dA/dt)1 – log(dA/dt)2} / {log [S]1 – log [S]2}.

An exactly analogous procedure yields the values of b and c.

Experimental Procedure

The following solutions are to be prepared from the stock solutions:

Volume of stock solution used /cm3

I II III IV
Cyclohexahone 20 20 20 14
HCl 10 10 6 10
Distilled Water 14 16 20 22
KI3 6 4 4 4

[Cyclohexanone] stock = 0.230 mol dm-3

[HCl] stock = 0.500 mol dm-3
[KI3] = 0.0360 mol dm-3

Mix the acid, ketone and water together in a 100 cm 3 conical flask. Label the
flask and place in the 303 K constant temperature bath and allow the flask

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and its content to equilibrate for at least 15 minutes. Thermostat the KI3 stock
solution as well.

After thermal equilibrium has been attained, the reaction is started by pipetting
the required amount of the KI3 solution into the flask. As soon as the pipette
has drained, the timer is started and the mixture mixed thoroughly and
returned to the bath. Immediately, a sample is transferred from the flask to a
spectrophotometer sample cell (using a dropper) and its absorbance
measured. The sample cell is then emptied, rinsed with distilled water, and
dried. Further samples are taken and measured at intervals of 2 minutes,
until sufficient points are obtained for giving a good plot of absorbance A
versus time.

Carry out the same procedure each of the mixture I, II, III and IV. Determine
the gradient of the each plot of absorbance A versus time.

Operation of the Spectrophotometer

The operation manual can be obtained from the lecturer-in-charge or the

Laboratory Assistant. Make sure you know how to operate the instrument (you
can ask the lecturer/demonstrator/lab. assistant for help).

Make sure you measure the absorbance of KI3 solution of 0.00360 mol dm-3 a
few times to obtain the best average value for l.

Calculations and Conclusion

The values of dA/dt for each experiment may be obtained readily from the
slopes of graphs of absorbance A as a function of time for each experiment.
The slopes should be determined by a graphical method, together with the
uncertainty analysis.

The uncertainties in the values of log dA/dt and log (concentration) are then
used to determine the uncertainties in the reaction orders obtained.

Using the value of l which you have determined, the rate constant k can be
calculated using equation (7) for each of the four runs (I)-(IV). The average
value and its standard deviation are then obtained. The mean value should be
compared with the literature value.

There are three mechanisms of reaction being proposed for the iodination of
cyclohexanone (Schemes A, B and C). Show whether the form of the rate
equation which you have determined is consistent with any of these. If so,
which step of the chosen mechanism is the rate-determining one?

Are your results consistent with the observation that the rate of bromination of
ketones is exactly the same as the rate of iodination?

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References:

1. G.W.Barrow, “Physical Chemistry”, 2nd Ed., McGraw-Hill, 1966

2. R.T.Morrison & R.N.Boyd, “Organic Chemistry”, Allyn & Bacon, 1959
3. P.W.Atkins, “Physical Chemistry”, 4th Ed., Oxford, 1994
4. I.N.Levine, “Physical Chemistry”, 4th Ed., McGraw-Hill, 1995
5. R.A.Alberty & R.J.Silbey, “Physical Chemistry”, 2nd Ed., John Wiley
1997.

PROPOSED MECHANISMS OF IODINATION OF CYCLOHEXANONE

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Physical Chemistry, Year 2, Laboratory Manual Experiment 7
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EXPERIMENT 7

DETERMINATION OF MEAN ACTIVITY COEFFICIENT AND SOLUBILITY

OF POTASSIUM HYDROGEN TARTARATE (KHT) IN AQUEOUS
SOLUTION AT 30°C

Background

The solubility of potassium hydrogen tartarate (KHT) in distilled water and in

aqueous sodium chloride solutions at concentrations 0.05, 0.10, 0.15 and
0.20 mol dm-3 are determined at 30 oC by the following method.

For the equilibrium dissociation reaction

KHT (s) ↔ K+ (aq) + HT - (aq)

it is assumed that the dissociation is complete, meaning that no overall neutral

ion pairs (K+…HT -) nor other reactions are present to reduce the apparent
number of ions in solution. The concentrations of the various species present
in units of M (moles dm-3 of solution) can be written

[K+] = c, [HT -] = c, [Na+] = m, [Cl -] = m

where the species within brackets […] refer to ionic concentrations. It is

further assumed that the sodium chloride salt fully dissociates. With these
assumptions, the ionic strength I for the single charged species mixture is
given by:-

[K + ] [HT- ] [Na ] [Cl ]

I c m.
2

The solubility constant for KHT, K s , is given by

2
Ks aK aHT [K ][HT ] K Cl
[K ][HT ] (1a)

which implies

Ks c2 2
(1b)

2
where by convention, K Cl ; is termed the mean activity coefficient
and theories provide various expressions to compute this quantity with varying
accuracy. For (1a), aK , aHT refers to the activity of the K+ and HT - ions
where in general aX [ X ] X for species X , where X is the activity
coefficient of the said species. It follows from (1a) that

log K s 2 log c 2 log (2)

where log here refers to base 10 logarithms ( log10 ).

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Physical Chemistry, Year 2, Laboratory Manual Experiment 7
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According to the extended Debye-Huckel theory (see reference [1]), is

determined from
AI 1/ 2
log bI (3)
(1 I 1/ 2 )

where b is a parameter and A is the Debye-Huckel constant with the value

A 0.5160 at 30 oC. Using (3) in (2) and rearranging leads to

2 AI 1/ 2
log K s' 2log c log K s 2bI (4)
(1 I 1/ 2 )

The expression in curly brackets in (4) is defined as log K s' and it can be
computed explicitly, and so (4) can be written as a linear form y mx d with
m the gradient and d the intercept, where

log K s' log K s 2bI . (5)

Plotting log K s' against I would produce a straight line graph with intercept
log K s and gradient 2b . Once K s has been determined, may be
determined for any concentration using (1(b)).

Experimental procedure

The experiment involves (a) preparing various saturated solutions of KHT in

differing concentrations of NaCl solution at 30 oC followed by (b) pipetting 10
ml aliquots of these prepared solutions to determine the HT - concentration
by titration with a standardized solution of sodium hydroxide which must be
prepared. Confirm that the stoichiometry of the sodium or potassium salt of
HT - in the neutralization reaction is HT - +OH - H 2 O+T 2- . To prevent
precipitation of KHT inside the pipette whenever solutions are drawn in, the
standardized pipette (calibrated by gravimetric determination of volume from
distilled water at 30oC) must be at the same temperature as the KHT solution.
This is achieved by immersing the pipettes in a tube containing distilled water
maintained at 30oC in a temperature-controlled water bath. A tube containing
a cotton filter is placed at the end of the pipette to prevent solid KHT from
being drawn into the pipette. Should the filter fail, your readings would be
adversely affected. You should prepare the cotton filters by washing the
cotton ball(s) or strands inserted into the tube several times with distilled
water by drawing the fluid into the pipette with the tube fitted at the end.
Devise a method to ensure that that the residual saturated solutions of KHT
inside the filter and the sides of the pipette do not affect the accuracy of your
results. Standardize the NaOH solution of approximately 0.04 M using
sodium hydrogen tartarate weighed out appropriately and dissolved into a
solution of known concentration; use phenolphthalein as an indicator. The
standard NaOH solution must be used as soon as possible after the
standardization procedure because it will react with the carbon dioxide
present in the air, changing its concentration in the process. As a preventive
measure, a drying tube containing solid pellets of NaOH may be placed at the
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top end of the burette which contains the standardized NaOH to arrest this
reaction process during titrations. All volumetric measurements for the making
up of solutions must be conducted at the temperature of the water bath
(30oC). Prepare 250 cm3 of stock NaCl solution of concentration 0.2000 M
using Analar grade NaCl. (‘Analar’ is an abbreviation for analytical reagent).
You have just precisely enough material to make 100 cm 3 NaCl solutions of
concentration 0.2000, 0.1500, 0.1000 and 0.0500 M from the stock solution by
appropriate dilution. To prepare a Y M 100 cm 3 solution from the stock
solution, dilute X cm3 of stock with distilled water to make up to 100 cm 3
where Y 100 X 0.2000 . Add excess KHT salt (meaning add until a residue
of undissolved KHT remains) to each of these solutions, which are individually
contained in stoppered conical flasks, and equilibrate them in the water bath
after shaking them for about 5 minutes. Repeat this process of shaking the
solution followed by equilibration several times until the total shake time is
about 20 minutes. At this point, place the flasks in the water bath for another
10 minutes without shaking. Pipette 10 ml aliquots of the solutions using the
cotton filter attached to the base of the pipette and titrate with the
standardized NaOH solution using phenolphthalein as the indicator. For each
of the four solutions prepared, a minimum of three titrations should be
performed until results consistent to within ± 0.05 cm3 NaOH solution volume
are obtained.

Results and Calculations

(i) Calculate the solubility c for KHT for each of the four solutions from the
titration results.
(ii) Determine log K s' and I for each of the solutions, and plot a graph of
log K s' vs. I . From the intercept, determine K s , the solubility constant (also
variously known as the solubility product constant, solubility equilibrium
constant…etc.).
(iii) Determine , the mean ionic activity coefficient for KHT for each of the
solutions using Eq. (1).
(iv) Determine b which features in Eq.(3) and (4). What is the physical
significance of this parameter and discuss the magnitude of the b
parameter that you obtain by comparing with the associated physical
variable from the experimental literature.
(v) Compute Go at 30 oC for the reaction KHT(s) ↔ K+(aq) +HT -(aq)
(vi) Plot as determined from the experiment and from the extended Debye-
Huckel equation against the ionic strength. Which is the more accurate
value for this quantity? Discuss also the relative differences in magnitude
for the two methods.

Reminder: For each of the above computations, you must provide error
estimates for the required quantities to one significant figure.

Questions:

(i) How would you determine H o (T ) and S o (T ) in general and in particular

when H o and S o are assumed independent of temperature in the
vicinity (±10oC) of 30oC?
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(ii) What assumptions are made regarding the activity of KHT (solid state) in
Calculation (5) above to compute Go ?

Reference

[1] P. W. Atkins, Physical Chemistry

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