[CH101] Determination of the Equilibrium Constant for a Chemical Reaction

[Practical 1]

BINDURA UNIVERSITY OF SCIENCE EDUCATION

CHEMISTRY DEPARTMENT

CH 101: PHYSICAL CHEMISTRY PRACTICALS

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[CH101] Determination of the Equilibrium Constant for a Chemical Reaction
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COURSE OUTLINE

The course is mainly designed to illustrate and reinforce the lectures

on:
Group I-the alkali metals
1. Introduction to Chemical Thermodynamics
2. Electrochemistry and Chemical Equilibria
3. Reaction Kinetcs

Practical Write-up
The write-up should have the format below.
BINDURA UNIVERSITY OF SCIENCE EDUCATION
Faculty of SCIENCE
CHEMISTRY DEPARTMENT
Student Name Reg . No. .
Course Code:
Course Description:
Practical No:
Practical Title:
Partner(s):
AIM(S)
OBJEVTIVE(S)
THEORY
APPARATUS/EQUIPMENT
METHOD/PROCEDURE (In past and passive tense)
RESULTS
TREATMENT OF RESULTS:
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(i) Statistical Analysis of results

(ii) Basic calculations as required by the experiment
POST- LAB QUESTIONS
DISCUSSION: Discussion of:
-Objective achievement
-Method(s):- suitability, limitations and possible solutions
-Comparison of the results with the theoretical or researches done
-Skills developed
-Recommendations
CONCLUSION
REFERENCES (At least five references, and pages read)

SUBMISSION

All practicals should be submitted before or on the day of the next practical of that course
that is, the practicals are to be submitted in week’s time.

SAMPLES SYNTHESISED
Dry samples should be handed in labeled tubes with your name, date, name of compound
and yield written on the label. They must be kept in a dessicator if are to be used in the
next practical.

EXPERIMENT 1:
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[CH101] Determination of the Equilibrium Constant for a Chemical Reaction
[Practical 1]

Determination of the Equilibrium Constant for a Chemical Reaction

Purpose

To determine equilibrium constant for the reaction of Fe3+ and SCN-

Objective
To use spectrophotometric method to determine the equilibrium constant.
An Overview
When chemical substances react, the reaction typically does not go to completion. Rather, the
system goes to some intermediate state in which both the reactants and products have
concentrations that do not change with time. Such a system is said to be in chemical equilibrium.
When in equilibrium at a particular temperature, a reaction mixture obeys the Law of Chemical
Equilibrium, which imposes a condition on the concentrations of reactants and products. This
condition is expressed in the equilibrium constant Kc for the reaction.
In this experiment we will study the equilibrium properties of the reaction between iron (III) ion
and thiocyanate ion:

Fe3+(aq) + SCN−(aq) FeSCN2+(aq) (1)

When solutions containing Fe3+ ion and thiocyanate ion are mixed, Reaction 1 occurs to some
extent, forming the FeSCN2+ complex ion, which has a deep red color. As a result of the reaction,
the equilibrium amounts of Fe3+ and SCN− will be less than they would have been if no reaction
occurred; for every mole of FeSCN2+ that is formed, one mole of Fe3+ and one mole of SCN−
will react. According to the Law of Chemical
Equilibrium, the equilibrium constant expression Kc for Reaction 1 is formulated as follows:

(2)

The value of Kc in Equation 2 is constant at a given temperature. This means that mixtures
containing Fe3 and SCN− will react until Equation 2 is satisfied, so that the same value of the Kc
will be obtained no matter what initial amounts of Fe3+ and SCN− were used. Our purpose in this
experiment will be to find Kc for this reaction for several mixtures made up in different ways,
and to show that Kc indeed has the same value in each of the mixtures. The reaction is a
particularly good one to study because Kc is of a convenient magnitude and the color of the
FeSCN2+ ion makes for an easy analysis of the equilibrium mixture.
The mixtures will be prepared by mixing solutions containing known concentrations of iron (III)
nitrate, Fe(NO3)3, and potassium thiocyanate, KSCN. The color of the FeSCN2+ ion formed will
allow us to determine its equilibrium concentration. Knowing the initial composition of a
mixture and the equilibrium concentration of FeSCN2+, we can calculate the equilibrium
concentrations of the rest of the pertinent species and then determine
Kc.
Since the calculations required in this experiment may not be apparent, we will go through a
step-by-step procedure by which they can be made. As a specific example, let us assume that we
prepare a mixture by mixing 10.0 mL of 2.00 × 10−3 M Fe(NO3)3 with 10.0 mL of 2.00 × 10−3 M
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KSCN. As a result of Reaction 1, some red FeSCN2+ ion is formed. By the method of analysis
described later, its concentration at equilibrium is found to be 1.50 × 10−4 M. Our problem is to
find Kc for the reaction from this information. To do this we first need to find the initial number
of moles of each reactant in the mixture. Second, we determine the number of moles of product
that were formed at equilibrium. Since the product was formed at the expense of reactants, we
can calculate the amount of each reactant that was used up. In the third step we find the number
of moles of each reactant remaining in the equilibrium mixture. Fourth, we determine the
concentration of each reactant. Finally, in the fifth step we evaluate Kc for the reaction.

Step 1 Finding the Initial Number of Moles of Each Reactant. This requires relating the
volumes
and concentrations of the reagent solutions that were mixed to the numbers of moles
of each reactant species in those solutions. By the definition of the molarity, MA, of a species
A,
(3)

Using Equation 3, it is easy to find the initial number of moles of Fe3+ and SCN−. For each
solution the volume used was 10.0 mL, or 0.0100 L. The molarity of each of the solutions was
2.00 × 10−3 M, so = 2.00 × 10−3 M and = 2.00 × 10−3 M. Therefore, in the reagent solutions, we
find that

initial no. moles Fe3+ = ×V = 2.00 × 10−3M × 0.0100 L = 20.0 × 10−6 moles
initial no. moles SCN−= ×V = 2.00 × 10−3M × 0.0100 L = 20.0 × 10−6 moles

Step 2 Finding the Number of Moles of Product Formed. Here again we can use Equation 3
to advantage. The concentration of FeSCN2+ was found to be 1.50 × 10−4 M at equilibrium. The
volume of the mixture at equilibrium is the sum of the two volumes that were mixed, and is
20.0 mL, or 0.0200 L. So,

no. moles FeSCN2+= ×V = 1.50 × 10−4M × 0.0200 L = 3.00 × 10−6 moles.

The number of moles of Fe3+ and SCN− that were used up in producing the FeSCN2+ must also
both be equal to 3.00 × 10−6 moles since, by Equation 1, it takes one mole Fe3+ and one mole
SCN− to make each mole of FeSCN2+.

Step 3 Finding the Number of Moles of Each Reactant Present at Equilibrium. In Step 1 we
determined that initially we had 20.0 × 10−6 moles Fe3+ and 20.0 × 10−6 moles SCN− present.
In Step 2 we found that in the reaction 3.00 × 10−6 moles Fe3+ and 3.00 × 10−6 moles
SCN− were used up. The number of moles present at equilibrium must equal the number we
started with minus the number that reacted. Therefore, at equilibrium,

no. moles at equilibrium = initial no. moles − no. moles used up

equil. no. moles Fe3+ = 20.0 × 10−6 − 3.00 × 10−6 = 17.0 × 10−6 moles (4)
equil. no. moles SCN− = 20.0 × 10−6 − 3.00 × 10−6 = 17.0 × 10−6 moles

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Step 4 Find the Concentrations of All Species at Equilibrium. Experimentally, we obtained

the concentration of FeSCN2+ directly. [FeSCN2+] = 1.50 × 10−4 M. The concentrations of Fe3+
and SCN− follow from Equation 3. The number of moles of each of these species at equilibrium
was obtained in Step 3. The volume of the mixture being studied was 20.0 mL, or
0.0200 L. So, at equilibrium,

Step 5 Finding the Value of Kc for the Reaction. Once the equilibrium concentrations of all
the reactants and products are known, one needs merely to substitute into Equation 2 to
determine Kc:

In this experiment you will obtain data similar to that shown in this example.
The calculations involved in processing that data are completely analogous to those we have
made. (Actually, your results will differ from the ones we obtained, since the data in our example
were obtained at a different temperature and so relate to a different value of Kc.)
In carrying out this analysis we made the assumption that the reaction which occurred was given
by
Equation 1. There is no inherent reason why the reaction might not have been

Fe3+(aq) + 2 SCN−(aq) Fe(SCN)2+(aq) (5)

If you are interested in matters of this sort, you might ask how we know whether we are actually
observing Reaction 1 or Reaction 5. The line of reasoning is the following. If Reaction 1 is
occurring, Kc for that reaction as we calculate it should remain constant with different reagent
mixtures. If, however, Reaction 5 is going on, Kc as calculated for that reaction should remain
constant. In the optional part of the Data and Calculations section, we will assume that Reaction
5 occurs and make the analysis of Kc on that basis. The results of the two sets of calculations
should make it clear that Reaction 1 is the one that we are studying.

Two analytical methods can be used to determine [FeSCN2+] in the equilibrium mixtures. The
more precise method uses a spectrophotometer, which measures the amount of light absorbed by
the red complex at 447 nm, the wavelength at which the complex most strongly absorbs. The
absorbance, A, of the complex is proportional to its concentration, M, and can be measured
directly on the spectrophotometer:

A = kM (6)

Your instructor will show you how to operate the spectrophotometer, if one is available in your
laboratory, and will provide you with a calibration curve or equation from which you can find
[FeSCN2+] once you have determined the absorbance of your solutions. See Appendix IV for
information about spectrophotometers.

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In the other analytical method a solution of known concentration of FeSCN2+ is prepared. The
[FeSCN2+] concentrations in the solutions being studied are found by comparing the color
intensities of these solutions with that of the known. The method involves matching the color
intensity of a given depth of unknown solution with that for an adjusted depth of known solution.
The actual procedure and method of calculation are discussed in the Experimental Procedure
section.
In preparing the mixtures in this experiment we will maintain the concentration of H+ ion at 0.5
M. The hydrogen ion does not participate directly in the reaction, but its presence is necessary to
avoid the formation of brown-colored species such as FeOH2+, which would interfere with the
analysis of [FeSCN2+].

Procedure
Label five regular test tubes (18 mm × 150 mm) 1 to 5, with labels or by noting their positions on
your test tube rack. Pour about 30 mL 2.00 × 10−3 M Fe(NO3)3 in 1 M HNO3 into a dry 100-mL
beaker. Pipet 5.00 mL of that solution into each test tube. Then add about 20 mL 2.00 × 10−3 M
KSCN to another dry 100-mL beaker. Pipet 1, 2, 3, 4, and 5 mL from the KSCN beaker into each
of the corresponding test tubes labeled
1 to 5. Then pipet the proper number of milliliters of water into each test tube to bring the total
volume in each tube to 10.00 mL. The volumes of reagents to be added to each tube are
summarized in Table 23.1, which you should complete by filling in the required volumes of
water. See Appendix IV for a discussion of the use of pipets.

Mix each solution thoroughly with a glass stirring rod. Be sure to dry the stirring rod after
mixing each solution.

Method I. Analysis by Spectrophotometric Measurement

Place a portion of the mixture in tube 1 in a spectrophotometer cell, as demonstrated by your

instructor, and measure the absorbance of the solution at 447 nm. Determine the concentration of
FeSCN2+ from the calibration curve provided for each instrument or from the equation furnished
to you. Record the value on the Data page.

Repeat the measurement using the mixtures in each of the other test tubes. For a discussion of
how absorbance and concentration are related, see Appendix IV.

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Method II. Analysis by Comparison with a Standard

Prepare a solution of known [FeSCN2+] by pipetting 10.00 mL 0.200 M Fe(NO3)3 in 1 M HNO3
into a test tube and adding 2.00 mL 0.00200 M KSCN and 8.00 mL water. Mix the solution
thoroughly with a stirring rod.

Since in this solution [Fe3+] >> [SCN−], Reaction 1 is driven strongly to the right. You can
assume without serious error that essentially all the SCN− added is converted to FeSCN2+.
Assuming that this is the case, calculate [FeSCN2+] in the standard solution and record the value
on the Data page.
The [FeSCN2+] in the unknown mixture in test tubes 1 to 5 can be found by comparing the
intensity of the red color in these mixtures with that of the standard solution. This can be done by
placing the test tube containing Mixture 1 next to a test tube containing the standard. Look down
both test tubes toward a wellilluminated piece of white paper on the laboratory bench.
Pour out the standard solution into a dry, clean beaker until the color intensity you see down the
tube containing the standard matches that which you see when looking down the tube containing
the unknown. Use a well-lit piece of white paper as your background. When the colors match,
the following relation is valid:

[FeSCN2+]unknown × depth of unknown solution = [FeSCN2+] × depth of standard solution (7)

Measure the depths of the matching solutions with a rule and record them. Repeat the
measurement for mixtures 2 through 5, recording the depth of each unknown and that of the
standard solution which matches it in intensity.

DISPOSAL OF REACTION PRODUCTS. In this experiment, reactant concentrations are

very low. In most localities you can pour the contents of the test tubes down the sink when you
have completed your measurements. However, consult your instructor for alternate disposal
procedures.

POST LAB QUESTIONS

Data and Calculations: Determination of the Equilibrium Constant for a Chemical Reaction

If Method II was used, [FeSCN2+]standard = ______________ × 10−4 M; [FeSCN2+] in Mixtures 1 to

5 is found by Equation 7.

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Processing the Data

A. Calculation of Kc assuming the reaction: Fe3+(aq) + SCN−(aq) FeSCN2+(aq) (1)

This calculation is most easily done by following Steps 1 through 5 in the discussion. Results are
to be entered in the table on the following page. If you are using Excel, set up the table as we
have, and follow the directions that follow.
Step 1 Find the initial number of moles of Fe3+ and SCN− in the mixtures in test tubes 1 through
5. Use Equation 3 and enter the values in the first two columns of the table.
Step 2 Enter the experimentally determined value of [FeSCN2+] at equilibrium for each of the
mixtures in the next to last column in the table. Use Equation 3 to find the number of moles of
FeSCN2+ in each of the mixtures, and enter the values in the fifth column of the table. Note that
this is also the number of moles of Fe3+ and SCN− that were used up in the reaction.

In calculating Kc in Part A, we assume, correctly, that the formula of the complex ion is
FeSCN2+. It is by no means obvious that this is the case and one might have assumed, for
instance, that Fe(SCN)2+ was the species formed. The reaction would then be
Fe3+(aq) + 2 SCN−(aq) Fe(SCN)2+(aq) (5)

If we analyze the equilibrium system we have studied, assuming that Reaction 5 occurs rather
than Reaction 1, we would presumably obtain nonconstant values of Kc. Using the same kind of
procedure as in Part A, calculate Kc for Mixtures 1, 3, and 5 on the basis that Fe(SCN)2+ is the
formula of the complex ion formed by the reaction between Fe3+ and SCN−. As a result of the
procedure used for calibrating the system by Method I or Method II, [Fe(SCN)2+] will equal one-
half the [FeSCN2+] obtained for each solution in Part A. Note that two moles SCN2 are needed to
form one mole Fe(SCN)2+. This changes the expression for Kc. Also, in calculating the
equilibrium number of moles SCN− you will need to subtract (2 × number of moles Fe(SCN)2+)
from the initial number of moles SCN−.

On the basis of the results of Part A, what can you conclude about the validity of the equilibrium
concept, as exemplified by Equation 2? What do you conclude about the formula of iron(III)
thiocyanate complex ion?

Advance Study Assignment: Determination of the Equilibrium Constant for a Chemical

Reaction

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1. A student mixes 5.00 mL 2.00 × 10−3 M Fe(NO3)3 with 3.00 mL 2.00 × 10−3 M KSCN. She

finds that in the equilibrium mixture the concentration of FeSCN2+ is 1.28 × 10−4 M. Find Kc

for the reaction

Fe3+(aq) + SCN−(aq) FeSCN2+(aq).

Step 1 Find the number of moles Fe3+ and SCN− initially present. (Use Eq. 3.)

____________ moles Fe3+; ____________ moles SCN−

Step 2 How many moles of FeSCN2+ are in the mixture at equilibrium? What is the volume of

the equilibrium mixture? (Use Eq. 3.)

____________ mL; ____________ moles FeSCN2+

How many moles of Fe3+ and SCN− are used up in making the FeSCN2+?

____________ moles Fe3+; ____________ moles SCN−

Step 3 How many moles of Fe3+ and SCN− remain in the solution at equilibrium? (Use Eq. 4

and the results of Steps 1 and 2.)

____________ moles Fe3+; ____________ moles SCN−

Step 4 What are the concentrations of Fe3+, SCN−, and FeSCN2+ at equilibrium? What is the

volume of the equilibrium mixture? (Use Eq. 3 and the results of Step 3.)

[Fe3+] = ____________ M; [SCN−] = ____________ M; [FeSCN2+] = ____________ M

____________ mL

Step 5 What is the value of Kc for the reaction? (Use Eq. 2 and the results of Step 4.)

Kc = ____________

2. Assume that the reaction studied in Problem 1 is Fe3+(aq) + 2 SCN−(aq) Fe(SCN)2+(aq).

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Find Kc for this reaction, given the data in Problem 1, except that the equilibrium concentration

of Fe(SCN)2+ is equal to 0.49 × 10−4 M.

a. Formulate the expression for Kc for the alternate reaction just cited.

b. Find Kc as you did in Problem 1; take due account of the fact that two moles SCN− are used up

per mole Fe(SCN)2+ formed.

Step 1 Results are as in Problem 1.

Step 2 How many moles of Fe(SCN)2 + are in the mixture at equilibrium? (You should use Eq.3.)

____________ moles Fe(SCN)2+

How many moles of Fe3+ and SCN− are used up in making the Fe(SCN)2+?

____________ moles Fe3+; ____________ moles SCN−

Step 3 How many moles of Fe3+ and SCN− remain in solution at equilibrium? Use the results of

Steps 1 and 2, noting that no. moles SCN− at equilibrium = original no. moles SCN− − (2 ×

no. moles Fe(SCN)2+).

____________ moles Fe3+; ____________moles SCN−

Step 4 What are the concentrations of Fe3+, SCN−, and Fe(SCN)2+ at equilibrium? (Use Eq. 3 and

the results of Step 3.)

[Fe3+] = __________ M; [SCN−] = __________ M; [Fe(SCN)2+] = __________ M

Step 5 Calculate Kc on the basis that the alternate reaction occurs. (Use the answer to Part 2a.)

Kc = ____________

References
1. Atkins P.W., de Paula, J. (2010), Physical Chemistry (9thed) Oxford University Press
2. Albert A. and Silbey J.S. (1997) Physical Chemistry (2nded) John Siley and Sons
3. Shaw D. J. and Avery H. E. (1991) Physical chemistry. MacMillan Education ltd
4. Artikins P.W, de Paula, J. (2010), Physical Chemistry 9th edition, Oxford University
Press
5. Levine I.N (1995), Physical Chemistry, 4th edition, McGraw-Hill Incorporation
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6. Noogle J.H (1996), Physical Chemistry, 3rd edition, Harper Collins

7. Barrow G.M (1996), Physical Chemistry, 6th edition, McGraw-Hill
8. Emil J. Slowinski, Wayne C. Wolsey, Robert C. Rossi (2012) Chemical Principles in
the Laboratory (10th ed.). Brooks/Cole, Belmont

EXPERIMENT 2:
HEAT OF NEUTRALISATION

Purpose: To calculate heat of neutralization and dilution

Objective: Determine the enthalpies of neutralization and dilution

Overview
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, ΔaH, is made up of the heat of
neutralization, ΔnH, and the heat of dilution of the sodium hydroxide solution, ΔdH. 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
ΔnH = ΔaH - ΔdH (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.

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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, ΔT is obtained as shown in Figure 1. The (corrected) heat produced, then, is

q = Cp ΔT (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 cm3 of distilled water (measured with a
graduated cylinder), using a current of 0.5A.

Neutralization of an acid
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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 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 cm3 of distilled water in place of the acid.

Calculations

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

Post Lab Questions

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?
References
1. Atkins P.W., de Paula, J. (2010), Physical Chemistry (9thed) Oxford University Press
2. Albert A. and Silbey J.S. (1997) Physical Chemistry (2nded) John Siley and Sons
3. Shaw D. J. and Avery H. E. (1991) Physical chemistry. MacMillan Education ltd
4. Artikins P.W , de Paula, J. (2010), Physical Chemistry 9th edition, Oxford University
Press
5. Levine I.N (1995), Physical Chemistry, 4th edition, McGraw-Hill Incorporation
6. Noogle J.H (1996), Physical Chemistry, 3rd edition, Harper Collins
7. Barrow G.M (1996), Physical Chemistry, 6th edition, McGraw-Hill
8. Emil J. Slowinski, Wayne C. Wolsey, Robert C. Rossi (2012) Chemical Principles in the
Laboratory (10th ed.). Brooks/Cole, Belmont

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EXPERIMENT 3:
Properties of Systems in Chemical Equilibrium—Le Châtelier’s Principle

Objective: To investigate the effect of changing a factor to a system at equillibrium

Overview
When working in the laboratory, one often makes observations that at first sight are surprising
and hard to explain. One might add a reagent to a solution and obtain a precipitate. Addition of
more of that reagent to the precipitate causes it to dissolve. A violet solution turns yellow on
addition of a reagent. Subsequent addition of another reagent brings back first a green solution
and then the original violet one. Clearly, chemical reactions are occurring, but how and why they
behave as they do is not at once obvious.

In this experiment we will examine and attempt to explain several observations of the sort we
have just mentioned. Central to our explanation will be recognition of the fact that chemical
systems tend to exist in a state of equilibrium. If one disturbs the equilibrium in one way or
another, the reaction may shift to the left or right, producing the kinds of effects we have
mentioned. If one can understand the principles governing the equilibrium system, it is often
possible to see how one might disturb the system, such as by adding a particular reagent or heat,
and so cause it to change in a desirable way.

Before proceeding to specific examples, let us examine the situation in a general way, noting the
key principle that allows us to make a system in equilibrium behave as we wish. Consider the
reaction
A(aq) B(aq) + C(aq) (1)

where A, B, and C are molecules or ions in solution. If we have a mixture of these species in
equilibrium, it turns out that their concentrations are not completely unrelated. Rather, there is a
condition that those concentrations must meet, namely that

(2)

where Kc is a constant, called the equilibrium constant for the reaction. For a given reaction at
any given temperature, Kc has a particular value.

When we say that Kc has a particular value, we mean just that. For example, we might find that,
for a given solution in which Reaction 1 can occur, when we substitute the equilibrium values for
the molarities of A, B, and C into Equation 2, we get a value of 10 for Kc. Now, suppose we add
more of species A to that solution. What will happen? Remember, Kc can’t change. If we
substitute the new higher molarity of A into Equation 2 we get a value that is smaller than Kc.
This means that the system is not in equilibrium, and must change in some way to get back to
equilibrium. How can it do this? It can do this by shifting to the right, producing more B and C
and using up some A. It must do this, and will, until the molarities of C, B, and A reach values
that, on substitution into Equation 2, equal 10. At that point the system is once again in
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equilibrium. In the new equilibrium state, [B] and [C] are greater than they were initially, and
[A] is larger than its initial value but smaller than if there had been no forced shift to the right.

The conclusion you should reach on reading the last paragraph is that one can always cause a
reaction to shift to the right by increasing the concentration of a reactant. An increase in
concentration of a product will force a shift to the left. By a similar argument we find that a
decrease in reactant concentration causes a shift to the left; a decrease in product concentration
produces a shift to the right. This is all true because Kc does not change (unless you change the
temperature). The changes in concentration that one can produce by adding particular reagents
may be simply enormous, so the shifts in the equilibrium system may also be enormous.
Much of the mystery of chemical behavior disappears once you understand this idea.
Another way one might disturb an equilibrium system is by changing its temperature. When this
happens, the value of Kc changes. It turns out that the change in Kc depends upon the enthalpy
change, ΔH, for the reaction.
If ΔH is positive, greater than zero (an “endothermic reaction”), Kc increases with increasing T. If
ΔH is negative (an “exothermic” reaction), Kc decreases with an increase in T. Let us return to
our original equilibrium between A, B, and C, where Kc equals 10. Let us assume that ΔH for
Reaction 1 is −40 kJ. If we raise the temperature, Kc will go down (ΔH < 0), say to a value of 1.
This means that the system will no longer be in equilibrium. Substitution of the initial values of
[A], [B], and [C] into Equation 2 produces a value that is too big, 10 instead of 1. How can the
system change itself to regain equilibrium? It must of necessity shift to the left, lowering [B] and
[C] and raising [A]. This will make the expression in Equation 2 smaller. The shift will continue
until the concentrations of A, B, and C, on substitution into Equation 2, give the expression a
value of 1.
From the discussion in the previous paragraph, you should be able to conclude that an
equilibrium system will shift to the left on being heated if the reaction is exothermic (ΔH < 0, Kc
decreases with temperature). It will shift to the right if the reaction is endothermic (ΔH > 0, Kc
increases with temperature). Again, since we can change temperatures very markedly, we can
shift equilibria a long, long way. An endothermic reaction that at 25 oC has an equilibrium state
that consists mainly of reactants might, at 1000 oC, exist almost completely as products.
The effects of concentration and temperature on systems in chemical equilibrium are often
summarized by Le Châtelier’s principle. The principle states that:
If you attempt to change a system in chemical equilibrium, it will react in such a way as to
counteract the change you attempted.
If you think about the principle for a while, you will see that it predicts the same kind of behavior
as we did by using the properties of Kc. Increasing the concentration of a reactant will, by the
principle, cause a change that decreases that concentration; that change must be a shift to the
right. Increasing the temperature of a reaction mixture will cause a change that tends to absorb
heat; that change must be a shift in the endothermic direction. The principle is an interesting one,
but does require more careful reasoning in some cases than the more direct approach we

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employed. For the most part we will find it more useful to base our arguments on the properties
of Kc.
In working with aqueous systems, the most important equilibrium is often that which involves
the dissociation of water into H+ and OH− ions:

H2O H+(aq) + OH−(aq) Kc = [H+] [OH−] = 1 × 10−14 (3)

In this reaction the concentration of water is very high and is essentially constant at about 55 M;
it is incorporated into Kc. The value of Kc is very small, which means that in any water system
the product of [H+] and [OH−] must be very small. In pure water, [ H+] equals [OH−] equals 1 ×
10−7 M.
Although the product, [H+] × [OH−] is small, that does not mean that both concentrations are
necessarily small. If, for example, we dissolve HCl in water, the HCl in the solution will
dissociate completely to H+ and Cl− ions; in 1 M HCl, [H+] will become 1 M, and there is
nothing that Reaction 3 can do about changing that concentration appreciably. Rather, Reaction 3
must occur in such a direction as to maintain equilibrium. It does this by lowering [OH−] by
reaction to the left; this uses up a little bit of H+ ion and drives [OH−] to the value it must have
when [H+] is 1 M, namely, 1 × 10−14 M. In 1 M HCl, [OH−] is a factor of ten million smaller than
it is in water. This makes the properties of 1 M HCl quite different from those of water,
particularly where H+ and OH− ions are involved. If we take 1 M HCl and add a solution of
NaOH to it, an interesting situation develops. Like HCl, NaOH is completely dissociated in
solution, so in 1 M NaOH, [OH−] is equal to 1 M. If we add 1 M NaOH to 1 M HCl, we will
initially raise [OH−] ions way above 1 × 10−14 M. However, Reaction 3 cannot be in equilibrium
when both [H+] and [OH−] are high; reaction must occur to re-establish equilibrium. The added
OH− ions react with H+ ions to form H2O, decreasing both concentrations until equilibrium is
established. If only a small amount of OH− ion is added, it will essentially all be used up; [H+]
will remain high, and [OH−] will still be very small, but somewhat larger than 10−14 M. If we add
OH− ion until the amount added equals in moles the
amount of H+ originally present, then Reaction 3 will go to the left until [H+] equals [OH−]
equals 1 × 10−7 M, and both concentrations will be very small. Further addition of OH− ion will
raise [OH−] to much higher values, easily as high as 1 M. In such a solution, [H+] would be very
low, 1 × 10−14 M. So, in aqueous solution, depending on the solutes present, we can have [H+]
and [OH−] range from about 1 M to 10−14 M, or 14 orders of magnitude. This will have a
tremendous effect on any other equilibrium system in which [H+] or [OH−] ions are reactants.
Similar situations arise in other equilibrium systems in which the concentration of a reactant or
product can be changed significantly by adding a particular reagent.
In many equilibrium systems, several equilibria are present simultaneously. For example, in
aqueous solution,
Reaction 3 must always be in equilibrium. There may, in addition, be equilibria between the
solutes in the aqueous solution. Some examples are those in Reactions 4, 5, 7, 8, 9, and 10 in the

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Experimental Procedure section. In some of those reactions, H+ and OH− ions appear; in others,
they do not. In Reaction 4, for example,
H+ ion is a product. The molarity of H+ in Reaction 4 is not determined by the indicator HMV,
since it is only present in a tiny amount. Reaction 4 will have an equilibrium state that is fixed by
the state of Reaction 3, which as we have seen depends markedly on the presence of solutes such
as HCl or NaOH. Reactions 8 and 9 can similarly be controlled by Reaction 3. Reactions 5 and 7,
which do not involve H+ or OH− ions, are not dependent on Reaction 3 for their equilibrium state.
Reaction 10 is sensitive to NH3 concentration and can be driven far to the right by addition of a
reagent such as 6 M NH3.
Experimental Procedure
In this experiment we will work with several equilibrium systems, each of which is similar to the
A-B-C system we discussed. We will alter these systems in various ways, forcing shifts to the
right and left by changing concentrations and temperature. You will be asked to interpret your
observations in terms of the principles we have presented.
A. Acid-Base Indicators
There is a large group of chemical substances, called acid-base indicators, which change color in
solution when [H+] changes. A typical substance of this sort is called methyl violet, which we
will give the formula HMV. In solution HMV dissociates as follows:
HMV(aq) H+(aq) + MV−(aq) (4) yellow violet
HMV has an intense yellow color, while the anion MV− is violet. The color of the indicator in
solution depends very strongly on [H+].
Step 1 Add about 5 mL of distilled water to a regular (18 × 150 mm) test tube. Add a few drops
of methyl violet indicator. Report the color of the solution on the Data page.
Step 2 How could you force the equilibrium system to go to the other form (color)? Select a
reagent that should do this and add it to the solution, drop by drop, until the color change
is complete.
If your reagent works, write its formula on the Data page. If it doesn’t, try another until you find
one that does. Work with 6 M reagents if they are available.
Step 3 Equilibrium systems are reversible. That is, the reaction can be driven to the left and right
many times by changing the conditions in the system. How can you force the system in
Step 2 to revert to its original color? Select a reagent that should do this and add it drop
by drop until the color has become the original one. Again, if your first choice was
incorrect, try another reagent. On the Data page write the formula of the reagent that was
effective.
Answer all the questions for Part A before going on to Part B.

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B. Solubility Equilibrium; Finding a Value for Ksp

Many ionic substances have limited water solubility. A typical example is PbCl2, which
dissolves to some
extent in water according to the reaction

PbCl2(s) Pb2+(aq) + 2 Cl−(aq) (5)

The equilibrium constant for this reaction takes the form

Kc = [Pb2+] × [Cl−]2 = Ksp (6)
The PbCl2 does not enter into the expression because it is a solid, and so has a constant effect on
the system, independent of its amount. The equilibrium constant for a solubility equilibrium is
called the solubility product, and is given the symbol Ksp.
For the equilibrium in Reaction 5 to exist, there must be some solid PbCl2 present in the system.
If there is no solid, there is no equilibrium; Equation 6 is not obeyed, and [Pb2+] × [Cl−]2 must be
less than the value of Ksp. If the solid is present, even in a tiny amount, then the values of [Pb2+]
and [Cl−] are subject to Equation 6.
Step 1 Set up a hot-water bath, using a 400-mL beaker half full of water. Start heating the water
with a burner while proceeding with Step 2.
Step 2 To a regular test tube add 5.0 mL 0.30 M Pb(NO3)2. In this solution [Pb2+] equals 0.30 M.

Add 5.0 mL 0.30 M HCl to a 10-mL graduated cylinder. In this solution [Cl−] equals
0.30 M.Add 1 mL of the HCl solution to the Pb(NO3)2 solution. Stir, and wait about 15
seconds. What happens? Record your result.
Step 3 To the Pb(NO3)2 solution add the HCl in 1-mL increments until a noticeable amount of
white solid PbCl2 is present after stirring. Record the total volume of HCl added at that
point.
Step 4 Put the test tube with the precipitate of PbCl2 into the hot-water bath. Stir for a few
moments. What happens? Record your observations. Cool the test tube under the cold-
water tap. What happens?
Step 5 Rinse out your graduated cylinder and then add about 5.0 mL of distilled water to the
cylinder. Add water in 1-mL increments to the mixture in the test tube, stirring well after each
addition. Record the volume of water added when the precipitate just dissolves. Answer the
questions and do the calculations in Part B before proceeding.
C. Complex Ion Equilibria
Many metallic ions in solution exist not as simple ions but, rather, as complex ions in
combination with other ions or molecules, called ligands. For example, the Co2+ ion in solution
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exists as the pink complex ion, and Cu2+ as the blue complex ion. In both of these ions the
ligands are H2O molecules.
Complex ions are reasonably stable but may be converted to other complex ions on addition of
ligands that form more stable complexes than the original ones. Among the common ligands that
may form complex species, OH−, NH3, and Cl− are important.
An interesting Co(II) complex is the ion, which is blue. This ion is stable in concentrated Cl−
solutions. Depending upon conditions, Co(II) in solution may exist as either or as . The
principles of chemical equilibrium can be used to predict which ion will be present:
(aq) + 4 Cl−(aq) (aq) + 6 H2O (7)
Step 1 Put a few small crystals (∼0.1 g) of CoCl2 ⋅ 6 H2O in a regular test tube. Add 2
mL of 12 M HCl.

Caution: This is a concentrated solution of an acidic gas; avoid contact with it and its
fumes. This is a concentrated strong acid with a choking odor.

Stir to dissolve the crystals. Record the color of the solution.

Step 2 Add 2-mL portions of distilled water, stirring after each dilution, until no further color
change occurs. Record the new color

Step 3 Place the test tube into the hot-water bath and note any change in color. Cool the tube
under the water tap and report your observations. Complete the questions in Part C before
continuing.
D. Dissolving Insoluble Solids
We saw in Part B that we can dissolve more PbCl2 by either heating its saturated solution or by
simply adding water. In most cases these procedures won’t work very well on other solids
because they are typically much less soluble than PbCl2.
There are, however, some very powerful methods for dissolving solids that depend on their
effectiveness upon the principles of equilibrium. As an example of an insoluble substance, we
might consider Zn(OH)2:

Zn(OH)2(s) Zn2+(aq) + 2 OH−(aq) Ksp = 5 × 10−17 = [Zn2+] × [OH−]−2 (8)

The equilibrium constant for Reaction 8 is very small, which tells us that the reaction does not go
very far to the right or, equivalently, that Zn(OH)2 is almost completely insoluble in water.
Adding a few drops of a solution containing OH− ion to one containing Zn2+ ion will cause
precipitation of Zn(OH)2.
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At first sight you might well wonder how one could possibly dissolve, say, 1 mole of Zn(OH)2 in
an aqueous solution. If, however, you examine Equation 8, you can see, from the equation for
Ksp, that in the saturated solution [Zn2+] × [OH−]2 must equal 5 × 10−17. If, by some means, we
can lower that product to a value below 5 × 10−17, then Zn(OH)2 will dissolve, until the product
becomes equal to Ksp, where equilibrium will again exist. To lower the product, we need to lower
the concentration of either Zn2+ or OH− very drastically. This turns out to be very easy to do. To
lower [OH−] we can add H+ ions from an acid. If we do that, we drive Reaction 3 to the left,
making [OH−] very, very small—small enough to dissolve substantial amounts of Zn(OH)2.

To lower [Zn2+] we can take advantage of the fact that zinc(II) forms stable complex ions with
both OH− and NH3:

Zn2+(aq) + 4 OH−(aq) Zn(OH)42− (aq) K1 = 3 × 1015 (9)

Zn2+(aq) + 4 NH3(aq) Zn(NH3)42+ (aq) K2 = 1 × 109 (10)

In high concentrations of OH− ion, Reaction 9 is driven strongly to the right, making [Zn2+] very
low. The same thing would happen in solutions containing high concentrations of NH3. In both
media we would therefore expect that Zn(OH)2 might dissolve, since if [Zn2+] is very low,
Reaction 8 must go to the right.
Step 1 To each of three small test tubes add about 2 mL 0.1 M Zn(NO3)2. In this
solution [Zn2+] equals 0.1 M. To each test tube add one drop 6 M NaOH
and stir. Report your observations.
Step 2 To the first tube add 6 M HCl drop by drop, with stirring. To the second
add 6 M NaOH, again drop by drop. To the third add 6 M NH3. Note what
happens in each case.
Step 3 Repeat Steps 1 and 2, this time using a solution of 0.1 M Mg(NO3)2.
Record your observations.

DISPOSAL OF REACTION PRODUCTS. The residues from Parts B and C should be

poured in the waste crock. Those from Parts A and D may be poured down the sink.

Post Lab Questions

Answer the questions in Part D.

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Data and Observations: Properties of Systems in Chemical Equilibrium

A. Acid-Base Indicators
1. Color of methyl violet in water ____________
2. Reagent causing color change ____________
3. Reagent causing shift back ____________. Explain, by considering how changes in [H+]
will cause
Reaction 4 to shift to right and left, why the reagents in Steps 2 and 3 caused the solution
to change color.
Note that Reactions 3 and 4 must both go to equilibrium after a reagent is added.
B. Solubility Equilibrium; Finding a Value for Ksp
2. Vol. 0.30 M Pb(NO3)2 = 5.0 mL No. moles Pb2+ = [M × V(stock)] = 1.5 × 10−3 moles
Observations:
3. Vol. 0.30 M HCl used ____________ mL No. moles Cl− added ____________ moles
4. Observations: in hot water ____________ in cold water ____________
5. Volume H2O added to dissolve PbCl2 ____________ mL
Total volume of solution ____________ mL
a. Explain why PbCl2 did not precipitate immediately on addition of HCl. (What condition
must be met by [Pb2+] and [Cl−] if PbCl2 is to form?)
b. Explain your observations in Step 4. (In which direction did Reaction 5 shift when
heated? What must have happened to the value of Ksp in the hot solution? What does this
tell you about the sign of ΔH in Reaction 5?)
c. Explain why the PbCl2 dissolved when water was added in Step 5. (What was the effect
of the added water on [Pb2+] and [Cl−]? In what direction would such a change drive
Reaction 5?)
References
1. Atkins P.W., de Paula, J. (2010), Physical Chemistry (9thed) Oxford University Press
2. Albert A. and Silbey J.S. (1997) Physical Chemistry (2nded) John Siley and Sons
3. Shaw D. J. and Avery H. E. (1991) Physical chemistry. MacMillan Education ltd
4. Artikins P.W, de Paula, J. (2010), Physical Chemistry 9th edition, Oxford University
Press
5. Levine I.N (1995), Physical Chemistry, 4th edition, McGraw-Hill Incorporation

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[CH101] Determination of the Equilibrium Constant for a Chemical Reaction
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6. Noogle J.H (1996), Physical Chemistry, 3rd edition, Harper Collins

7. Barrow G.M (1996), Physical Chemistry, 6th edition, McGraw-Hill
8. Emil J. Slowinski, Wayne C. Wolsey, Robert C. Rossi (2012) Chemical Principles in the
Laboratory (10th ed.). Brooks/Cole, Belmont

EXPERIMENT 4:
Rates of Chemical Reactions, II. A Clock Reaction

Aim: To determine the effect of temperature on the rate of reaction.

Objective(s): To calculate the rate constant(K), order of reaction and activation energy(Ea).

Overview
In the previous experiment we discussed the factors that influence the rate of a chemical reaction
and presented the terminology used in quantitative relations in studies of the kinetics of chemical
reactions. That material is also pertinent to this experiment and should be studied before you
proceed further.

This experiment involves the study of the rate properties, or chemical kinetics, of the following
reaction between iodide ion and bromate ion under acidic conditions:

6 I−(aq) + BrO3−(aq) + 6 H+(aq) → 3 I2(aq) + Br−(aq) + 3 H2O (1)

This reaction proceeds reasonably slowly at room temperature, its rate depending on the
concentrations of the I−, BrO3−, and H+ ions according to the rate law discussed in the previous
experiment. For this reaction the rate law takes the form

rate = k(I−)m(BrO3−)n(H+)p (2)

One of the main purposes of this experiment will be to evaluate the rate constant k and the
reaction orders m, n, and p for this reaction. We will also investigate the manner in which the
reaction rate depends on temperature, and will evaluate the activation energy of the reaction, Ea.
Our method for measuring the rate of the reaction involves what is frequently called a clock
reaction. In addition to Reaction 1, whose kinetics we will study, the following reaction will also
be made to occur simultaneously in the reaction flask:

I2(aq) + 2 S2O32−(aq) → 2 I−(aq) + S4O62−(aq) (3)

As compared with Equation 1 this reaction is essentially instantaneous. The I2 produced in (1)
reacts completely with the thiosulfate, S2O32−, ion present in the solution, so that until all the
thiosulfate ion has reacted, the concentration of I2 is effectively zero. As soon as the S2O32− is
gone from the system, the I2 produced by

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(1) remains in the solution and its concentration begins to increase. The presence of I2 is made
strikingly apparent by a starch indicator that is added to the reaction mixture, since I2 even in
small concentrations reacts with starch solution to produce a deep blue color.

By carrying out Reaction 1 in the presence of S2O32− and a starch indicator, we introduce a
“clock” into the system. Our clock tells us when a given amount of BrO3− ion has reacted (1/6
mole BrO3− per mole S2O32−), which is just what we need to know, since the rate of reaction can
be expressed in terms of the time it takes for a particular amount of BrO3− to be used up. In all
our reactions, the amount of BrO3− that reacts in the time we measure will be constant and small
as compared to the amounts of any of the other reactants. This means that the concentrations of
all reactants will be essentially constant in Equation 2, and hence so will the rate during each
reaction.

In our experiment we will carry out the reaction between BrO3−, I−, and H+ ions under different
concentration conditions. Measured amounts of each of these ions in aqueous solution will be
mixed in the presence of a constant, small amount of S2O32−. The time it takes for each mixture to
turn blue will be measured. The time obtained for each reaction will be inversely proportional to
its rate. By changing the concentration of one reactant and keeping the other concentrations
constant, we can investigate how the rate of the reaction varies with the concentration of a
particular reactant. Once we know the order for each reactant we can determine the rate constant
for the reaction.

In the last part of the experiment we will investigate how the rate of the reaction depends on
temperature. You will recall that in general the rate increases sharply with temperature. By
measuring how the rate varies with temperature we can determine the activation energy, Ea, for
the reaction by making use of the Arrhenius equation:

(4)

In this equation, k is the rate constant at the Kelvin temperature T, Ea is the activation energy,

and R is the gas constant. By plotting ln k against we should obtain, by Equation 4, a straight

line whose slope equals .

From the slope of that line we can easily calculate the activation energy.

Experimental Procedure

Safety: Wear your safety glasses while performing this experiment

A. Dependence of Reaction Rate on Concentration

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In Table 21.1 we have summarized the reagent volumes to be used in carrying out the several
reactions whose rates we need to know to find the general rate law for Reaction 1. First, measure
out 100 mL of each of the listed reagents (except H2O) into clean, labeled flasks or beakers. Use
these reagents in your reaction mixtures.

Table 21.1

The actual procedure for each reaction mixture will be much the same, and we will describe it
now for
Reaction Mixture 1.
Since there are several reagents to mix, and since we don’t want the reaction to start until we are
ready, we will put some of the reagents into one flask and the rest into another, selecting them so
that no reaction occurs until the contents of the two flasks are mixed. Using a 10-mL graduated
cylinder to measure volumes, measure out 10 mL 0.010 M KI, 10 mL 0.0010 M Na2S2O3, and 10
mL distilled water into a 250-mL Erlenmeyer flask (Reaction Flask I). Then measure out 10 mL
0.040 M KBrO3 and 10 mL 0.10 M HCl into a 125-mL Erlenmeyer flask (Reaction Flask II). To
Flask II add three or four drops of starch indicator solution.

Pour the contents of Reaction Flask II into Reaction Flask I and swirl the solutions to mix them
thoroughly. Note the time at which the solutions were mixed. Continue swirling the solution. It
should turn blue in less than 2 minutes. Note the time at the instant that the blue color appears.
Record the temperature of the blue solution to 0.2°C.
Repeat the procedure with the other mixtures in Table 21.1. Don’t forget to add the
indicator before mixing the solutions in the two flasks. The reaction flasks should be rinsed with
distilled water between runs. When measuring out reagents, rinse the graduated cylinder with
distilled water after you have added the reagents to Reaction Flask I, and before you measure out
the reagents for Reaction Flask II. Try to keep the temperature just about the same in all the runs.
Repeat any experiments that did not appear to proceed properly.

B. Dependence of Reaction Rate on Temperature

In this part of the experiment, the reaction will be carried out at several different temperatures,
using Reaction Mixture 1 in all cases. The temperatures we will use will be about 20°C, 40°C,
10°C, and 0°C.

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We will take the time at about 20°C to be that for Reaction Mixture 1 as determined at room
temperature. To determine the time at 40°C proceed as follows. Make up Reaction Mixture 1 as
you did in Part A, including the indicator. However, instead of mixing the solutions in the two
flasks at room temperature, put the flasks into water at 40°C, drawn from the hot-water tap into
one or more large beakers. Check to see that the water is indeed at about 40°C, and leave the
flasks in the water for several minutes to bring them to the proper temperature.
Then mix the two solutions, noting the time of mixing. Continue swirling the reaction flask in the
warm water. When the color change occurs, note the time and the temperature of the solution in
the flask.

Repeat the experiment at about 10°C, cooling all the reactants in water at that temperature before
starting the reaction. Record the time required for the color to change and the final temperature
of the reaction mixture. Repeat once again at about 0°C, this time using an ice-water bath to cool
the reactants.

C. Dependence of the Reaction Rate on the Presence of Catalyst

Some ions have a pronounced catalytic effect on the rates of many reactions in water solution.
Observe the effect on this reaction by once again making up Reaction Mixture 1. Before mixing,
add one d
rop 0.5 M (NH4)2MoO4, ammonium molybdate, and a few drops of starch indicator to Reaction
Flask II. Swirl the flask to mix the catalyst thoroughly. Then mix the solutions, noting the time
required for the color to change.

Disposal of reaction products: The reaction products in this experiment are very dilute and
may be poured into the sink as you complete each part of the experiment if so directed by
your instructor.

Post Lab Questions

Data and Calculations: Rates of Chemical Reactions,

II. A Clock Reaction

A. Dependence of Reaction Rate on Concentration

Reaction: 6 I−(aq) + BrO3−(aq) + 6 H+(aq) → 3 I2(aq) + Br−(aq) + 3 H2O (1)

rate = k(I−)m(BrO3−)n(H+)p = (2)

In all the reaction mixtures used in this experiment, the color change occurred when a constant
predetermined number of moles of BrO3− had been used up by the reaction. The color “clock”
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allows you to measure the time required for this fixed number of moles of BrO3− to react. The
rate of each reaction is determined by the time t required for the color to change; since in
Equation 2 the change in concentration of BrO3− ion, Δ(BrO3−), is the same in each mixture, the
relative rate of each reaction is inversely proportional to the time t. Since we are mainly
concerned with relative rather than absolute rate, we will for convenience take all relative rates
as being equal to 1000/t. Fill in the following table, first calculating the relative reaction rate for
each mixture.

The reactant concentrations in the reaction mixture are not those of the stock solutions, since the
reagents were diluted by the other solutions. The final volume of the reaction mixture is 50 mL
in all cases. Since the number of moles of reactant does not change on dilution we can say, for
example, for I− ion, that
no. moles I− = (I−)stock × Vstock = (I−)mixture × Vmixture
For Reaction Mixture 1,
(I−)stock = 0.010 M, Vstock = 10 mL, Vmixture = 50 mL
Therefore,

Calculate the rest of the concentrations in the table using the same approach.

Determination of the Orders of the Reaction

Given the data in the table, the problem is to find the order for each reactant and the rate constant
for the reaction. Since we are dealing with relative rates, we can modify Equation 2 to read as
follows:
relative rate = k’(I−)m(BrO3−)n(H+)p (5)

We need to determine the relative rate constant k′ and the orders m, n, and p in such a way as to
be consistent with the data in the table.
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The solution to this problem is quite simple, once you make a few observations on the reaction
mixtures. Each mixture (2 to 4) differs from Reaction Mixture 1 in the concentration of only one
species (see table). This means that for any pair of mixtures that includes Reaction Mixture 1,
there is only one concentration that changes. From the ratio of the relative rates for such a pair of
mixtures we can find the order for the reactant whose concentration was changed. Proceed as
follows.
Write Equation 5 below for Reaction Mixtures 1 and 2, substituting the relative rates and the
concentrations of I−, BrO3−, and H+ ions from the table you have just completed.
Relative Rate 1 = ____________ = k′( )m( )n( )p
Relative Rate 2 = ____________ = k′( )m( )n( )p
Divide the first equation by the second, noting that nearly all the terms cancel out. The result is
simply

If you have done this properly, you will have an equation involving only m as an unknown.
Solve this equation for m, the order of the reaction with respect to I− ion.
m = ____________ (nearest integer)
Applying the same approach to Reaction Mixtures 1 and 3, find the value of n, the order of the
reaction with respect to BrO3− ion.
Relative Rate 1 = ____________ = k′( )m( )n( )p
Relative Rate 3 = ____________ = k′( )m( )n( )p
Dividing one equation by the other:
=
n = ____________
Now that you have the idea, apply the method once again, this time to Reaction Mixtures 1 and
4, and find p, the order with respect to H+ ion.
Relative Rate 4 = k′( )m( )n( )p
Dividing the equation for Relative Rate 1 by that for Relative Rate 4, we get
=
p = ____________
Having found m, n, and p (nearest integers), the relative rate constant, k′, can be calculated by
substitution of m, n, p, and the known rates and reactant concentrations into Equation 5. Evaluate
k′ for Reaction Mixtures 1 to 4.
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Reaction 1 2 3 4
k′ ____________ ____________ ____________ ____________ k′ave ____________
Standard deviation in k'____________ (See Appendix VIII)
Why should k′ have nearly the same value for each of the above reactions?
Using k′ave in Equation 5, predict the relative rate and time, tpred, for Reaction Mixture 5. Use the
concentrations in the table.
Relative ratepred ____________ tpred ____________ tobs ____________
B. Effect of Temperature on Reaction Rate: The Activation Energy
To find the activation energy for the reaction it will be helpful to complete the following table.
The dependence of the rate constant, k′, for a reaction is given by Equation 4:

(4)

Since the reactions at the different temperatures all involve the same reactant concentrations, the
rate constants,
k′, for two different mixtures will have the same ratio as the reaction rates themselves for the two
mixtures.
This means that in the calculation of Ea, we can use the observed relative rates instead of rate
constants.
Proceeding as before, calculate the relative rates of reaction in each of the mixtures and enter
these values in
(c). Take the ln rate for each mixture and enter these values in (d). To set up the terms in 1/T, fill
in (b), (e), and (f) in the table.
Approximate Temperature in °C
20 40 10 0
(a) Time t in seconds for color to appear ________ ________ ________ ________
(b) Temperature of the reaction mixture in °C ________ ________ ________ ________
(c) Relative rate = 1000/t ________ ________ ________ ________
(d) lkikkjnn of relative rate ________ ________ ________
________
(e) Temperature T in K ________ ________ ________ ________
(f) 1/T, K−1 ________ ________ ________ ________
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To evaluate Ea, make a graph of ln relative rate vs. 1/T, using Excel or the graph paper provided.
(For more help on using excel ask your lecturer/Teaching Assistant).
Find the slope of the line obtained by drawing the best straight line through the experimental
points.
Slope = ____________
The slope of the line equals −Ea/R, where R = (8.31 joules/mole K) if Ea is to be in joules per
mole. Find the activation energy, Ea, for the reaction.
C. Effect of a Catalyst on Reaction Rate
Catalyzed
Reaction 1 Reaction 1
Time for color to appear (seconds) ____________ ____________
Would you expect the activation energy, Ea, for the catalyzed reaction to be greater than, less
than, or equal to the activation energy for the uncatalyzed reaction? Why?

References
1. Atkins P.W., de Paula, J. (2010), Physical Chemistry (9thed) Oxford University Press
2. Albert A. and Silbey J.S. (1997) Physical Chemistry (2nded) John Siley and Sons
3. Shaw D. J. and Avery H. E. (1991) Physical chemistry. MacMillan Education ltd
4. Artikins P.W , de Paula, J. (2010), Physical Chemistry 9th edition, Oxford University
Press
5. Levine I.N (1995), Physical Chemistry, 4th edition, McGraw-Hill Incorporation
6. Noogle J.H (1996), Physical Chemistry, 3rd edition, Harper Collins
7. Barrow G.M (1996), Physical Chemistry, 6th edition, McGraw-Hill
8. Emil J. Slowinski, Wayne C. Wolsey, Robert C. Rossi (2012) Chemical Principles in
the Laboratory (10th ed.). Brooks/Cole, Belmont

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EXPERIMENT 5:
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:-

where by convention, ; is termed the mean activity coefficient and theories

provide various expressions to compute this quantity with varying accuracy. For (1a), refers to
the activity of the K+ and HT- ions where in general for species, where is the activity coefficient
of the said species. It follows from (1a) that

(2)
where here refers to base 10 logarithms (log10 ). According to the extended Debye-Huckel theory
(see reference [1]), γ± is determined from

(3)
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
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(4)
The expression in curly brackets in (4) is defined as ' log s K 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 2 HT- +OH H2O+T2-. 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 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 cm3
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 cm3 solution from the stock solution, dilute X cm3 of
stock with distilled water to make up to 100 cm3 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
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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 γ±, the mean ionic activity, coefficient γ± 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 ΔG o at 30 oC for the reaction KHT(s) ↔ K+(aq) +HT-(aq)
(vi) Plot γ± 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.
Post Lab Questions:
(i) How would you determine ΔHo(T) and ΔSo(T) in general and in particular when ΔHo and
ΔSo are assumed independent of temperature in the vicinity (±10oC) of 30oC?
(ii) What assumptions are made regarding the activity of KHT (solid state) in Calculation (5)
above to compute ΔGo?
Reference
1. Atkins P.W., de Paula, J. (2010), Physical Chemistry (9thed) Oxford University Press
2. Albert A. and Silbey J.S. (1997) Physical Chemistry (2nded) John Siley and Sons
3. Shaw D. J. and Avery H. E. (1991) Physical chemistry. MacMillan Education ltd
4. Artikins P.W, de Paula, J. (2010), Physical Chemistry 9th edition, Oxford University
Press

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[CH101] Determination of the Equilibrium Constant for a Chemical Reaction
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5. Levine I.N (1995), Physical Chemistry, 4th edition, McGraw-Hill Incorporation

6. Noogle J.H (1996), Physical Chemistry, 3rd edition, Harper Collins
7. Barrow G.M (1996), Physical Chemistry, 6th edition, McGraw-Hill
8. Emil J. Slowinski, Wayne C. Wolsey, Robert C. Rossi (2012) Chemical Principles in the
Laboratory (10th ed.). Brooks/Cole, Belmont

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