Determination of Mole Relationships

in a Chemical Reaction
A balanced chemical equation gives the mole ratios of the reactants and the products as coefficients. When
some of the chemical formulas are not known, an experiment must be conducted to help determine the mole
ratios.

This experiment uses two common substances as the reactants: hypochlorite ion (OCl) from household
bleach and thiosulfate ion (S2O32), the active ingredient in a photographic fixer solution used to develop
film. In the reaction, hypochlorite ions oxidize the thiosulfate ions according to the unbalanced and
incomplete reaction equation below.
A OCl + B S2O32 products
It is possible to identify the coefficients, A and B, for the reactants, without knowing the products of the
reaction. The process that you will use to determine the coefficients is called continuous variations. You will
prepare a series of mixtures of the two reactants. Each mixture will have the same total volume and since the
concentrations of the reactants are equimolar, the same total number of moles of reactants. The reaction is
exothermic, thus the mixture generating the most heat energy will be the reaction that completely consumes
both the hypochlorite and the thiosulfate ions leaving no excess reactant. You will collect maximum
temperatures for each trial, determine the total temperature change for each trial, and then graph your data in
order to establish the optimum mole to mole ratio and thus establish the coefficients for the reaction.

OBJECTIVES
In this experiment, you will
Measure the enthalpy change of a series of reactions using the method of continuous variations.
Determine the stoichiometry of an oxidation-reduction reaction in which the reactants are known but
the products are unknown.

Figure 1

MATERIALS
Data collection apparatus 0.50 M NaOCl solution (200 mL per lab group)
computer or handheld 0.50 M Na2S2O3 solution in 0.2 M NaOH
Temperature Probe (200 mL per lab group)
2 burets for dispensing reactants three 250 mL beakers
ring stand with buret clamp polystyrene cups

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

PROCEDURE
1. Obtain and wear goggles.

2. Set up the data collection system. Connect an interface to the computer or handheld with the proper
cable.
a. Connect a Temperature Probe to the interface.
b. Start the data collection program.
c. The default time graph and preset run time are sufficient for this experiment.
3. Obtain about 200 mL of each of the reactant solutions.

4. Use the dispensing burets set up by your teacher to measure out precisely 25.0 mL of the 0.50 M
NaOCl solution into a polystyrene cup. If you miss the 25.0 mL mark, just record your volume exactly
and take extra care with the next measurement since you need to obtain the same total volume for each
trial. Nest the cup in a beaker to help stabilize the cup (see Figure 1).

5. Immerse the tip of the Temperature Probe in the polystyrene cup of NaOCl solution.

6. Measure out precisely 25.0 mL of the 0.50 M Na2S2O3 solution into a beaker. Do not mix the two
solutions yet.

7. Start the data collection. Let the program gather and graph a few initial temperature readings, and
then add the Na2S2O3 solution. Gently stir the reaction mixture with the Temperature Probe.

8. Examine the data to calculate and record the maximum temperature change.

9. Rinse out and dispose of the reaction mixture as directed.

10. Continue testing various ratios of the two solutions, keeping the total volume constant, until you have
three measurements on either side of the ratio that produced the greatest temperature change.

DATA TABLE
Volume OCl Volume S2O32 Temperature change
Trial (C)
(mL) (mL)

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

PRE-LAB QUESTIONS
1. What is the total reaction volume for this procedure?

2. Predict the sign of H for this reaction. Justify your prediction.

3. Using the set of axes provided below, properly label the y-axis and sketch the curve that you expect to
see at the end of a given trial. Explain how you will use the graph to determine the maximum
temperature change.

Time (s)

4. Explain how you will use this curve to determine the maximum temperature change for a given trail.

5. A student conducts this experiment using two equimolar reactants, X &Y, and obtains the data shown
in the table below. The optimum mole to mole ratio requires that you plot the temperature change
recorded for each trial vs. the volume of X reacting. Your graph should have a maximum, but that
maximum may not coincide with the optimum mole:mole ratio of reactants X:Y. In order to determine
the optimum ratio, perform two linear regressions for the temperature change vs. volume of reactant X
data. One regression will have a positive slope while the other will have a negative slope. Both
regressions will involve all the points on the portion of the graph that approaches the maximum. The
optimum volume for reactant X is obtained by interpreting the point where the two regression lines
intersect. Once you have established the simplest whole number optimum ratio for the reactants, write
the moles of reactant X that react completely with reactant Y in the space provided below the data table.
Volume Volume Temperature
Reactant X Reactant Y Change
(mL) (mL) (C)

25.0 25.0 24.9

30.0 20.0 33.0
20.0 30.0 19.8
40.0 10.0 22.3
10.0 40.0 7.8
45.0 5.0 14.1
43.0 7.0 18.0
___moles of X react with ___moles of
Y

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

POST-LAB QUESTIONS AND DATA ANALYSIS

1. Use graphical methods to determine the whole number mole ratio of the two reactants in this
experiment.

2. Why must the total volume of the solution mixture be kept constant in all trials?

3. The molarities of the reactant solutions were equal in this experiment. Is this necessary, or even
important, for the success of the experiment?

4. Identify the limiting reactant for each trial that you performed.

5. Write the balanced oxidation-reduction reaction for the reaction of OCl and S2O32 in basic solution.
Does the mole ratio that you determined in your experiment match the actual reaction equations
coefficients?

6. Suggest a measurement other than the temperature change that could be used in an experiment
involving the method of continuous variations that could be used to determine the mole ratios for a pair
of reactants.

7. Why is it more accurate to use the point of intersection of the two lines to find the mole ratio rather
than the ratio associated with the greatest temperature change?

8. A student mixes two solutions that are not at the same initial temperature. If , 20 mL of Solution A at
23C is mixed with 30 mL of Solution B at 30C, suggest a method for making a correction so that the
student does not have to repeat the experiment.

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

TEACHER INFORMATION
1. This experiment conforms to the guidelines for the ninth laboratory experiment listed in the College
Board AP Chemistry guide (the Acorn Book). It can be conducted with a temperature probe or any
digital thermometer. It is suitable for Pre-AP students and is best performed in first-year chemistry.

2. Prepare the 0.50 M NaClO solution by diluting 745 mL of fresh bleach with distilled water to a total
volume of 1.0 L. Grocery store laundry bleach works well, but do not use bleach labeled "color safe".
Most commercial bleaches are labeled as 5.25% NaClO by mass, which is approximately 0.67 M. Note:
If you use bleach labeled "Ultra", the NaClO concentration is 6%. Prepare the 0.50 M NaClO solution by
diluting 653 mL of Ultra bleach with distilled water to a total volume of 1.0 L.

3. Prepare the 0.50 M Na2S2O3 solution in three steps. To make 1.0 L of solution, first dissolve 124 grams of
Na2S2O3 5 H2O (or 79.1 g of anhydrous Na2S2O3) in 500 mL of distilled water. Then add 8 g of solid
NaOH and stir the mixture to dissolve the NaOH. Lastly, add distilled water to make 1.0 L of solution.
Set up stations of dispensing burets for both NaClO and NaS2O3 solutions to increase student accuracy
and efficiency. Make your solutions at least the day before so they have a chance to thermally
equilibrate.

4. The laboratory technique used in this experiment is called continuous variations, in which a series of
reactions is conducted using various ratios of the reactants. The temperature change of the exothermic
reaction is measured and recorded for each ratio. The optimum ratio produces the greatest amount of heat
energy, thus the greatest change in temperature.

5. The solution volumes are measured with a graduated cylinder. The solutions are mixed in a polystyrene
cup and the temperature change is measured with the precision allowed by the Stainless Steel
Temperature Probe (0.1 C) or a digital thermometer.

6. One 50 minute lab period is sufficient to complete the experiment. It is a good idea for your students
to plot their results on a graph as they complete each trial, in case they need to conduct additional trials.
This can be done quite easily when collecting data using Logger Pro on a computer; data can be
manually entered into a graphing calculator or graphing software as well.

HAZARD ALERTS

Sodium thiosulfate: Slightly toxic by ingestion; body tissue irritant. Hazard code: CSomewhat hazardous.

Sodium hypochlorite solution: Corrosive liquid; causes skin burns; reacts with acid to evolve chlorine gas;
evolves chlorine when heated; moderately toxic by ingestion and inhalation; avoid contact with organic
material. Hazard code: BHazardous.

Sodium hydroxide: Corrosive solid; skin burns are possible; much heat evolves when added to water; very
dangerous to eyes; wear face and eye protection when using this substance. Wear gloves. It deserves the
instructors special handling and storage attention. Hazard Code: BHazardous.

The hazard information reference is: Flinn Scientific, Inc., Chemical and Biological Catalog Reference
Manual, P.O. Box 219, Batavia, IL 60510, (800) 452-1261, www.flinnsci.com

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

SAMPLE DATA
Volume OCl Volume S2O32 Temperature change
Trial
(mL) (mL) (C)

1 25.0 25.0 19.8

2 20.0 30.0 15.0

3 30.0 20.0 23.3

4 10.0 40.0 7.8

5 40.0 10.0 32.0

6 45.0 5.0 12.7

7 43.0 7.0 21.1

Answers to PRE-LAB QUESTIONS

1. What is the total reaction volume for this procedure?

50 mL; students have to read the procedure through step 6 to answer this correctly.

2. Predict the sign of H for this reaction. Justify your prediction.

H since the introduction states the reaction is exothermic. Students may also explain that heat energy
left the system, thus the negative sign on H.

3. Using the set of axes provided below, properly label the y-axis and sketch the curve that you expect to
see at the end of a given trial. Explain how you will use the graph to determine the maximum
temperature change.
Maximum Temperature

Temperature (C)

Time (s)

4. Explain how you will use this curve to determine the maximum temperature change for a given trial.

The procedure asks students to record a few temperature data points before mixing the solutions. This
allows for an initial temperature of the NaOCl solution to be established. As the reaction proceeds, the
temperature increases and levels off at a maximum. Students may take data long enough to even see a
decline in temperature as illustrated in red on the graph above.

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

5. A student conducts this experiment using two equimolar reactants, X &Y, and obtains the data shown
in the table below. The optimum mole to mole ratio requires that you plot the temperature change
recorded for each trial vs. the volume of X reacting. Your graph should have a maximum, but that
maximum may not coincide with the optimum mole:mole ratio of reactants X:Y. In order to determine
the optimum ratio, perform two linear regressions for the temperature change vs. volume of reactant X
data. One regression will have a positive slope while the other will have a negative slope. Both
regressions will involve all the points on the portion of the graph that approaches the maximum. The
optimum volume for reactant X is obtained by interpreting the point where the two regression lines
intersect. Once you have established the simplest whole number optimum ratio for the reactants, write
the moles of reactant X that react completely with reactant Y in the space provided below the data table.

Volume Volume Temperature

Reactant X Reactant Y Change
(mL) (mL) (C)

25.0 25.0 24.9

30.0 20.0 33.0
20.0 30.0 19.8
40.0 10.0 22.3
10.0 40.0 7.8
45.0 5.0 14.1
43.0 7.0 18.0
_3_ moles of X react with _2_moles of Y

6. Is there enough data to make a valid

conclusion? Justify your answer.

Yes. There are at least three data points

on each side of the maximum. Two points define a straight line,
but using three points assures that the values fall on a straight line.

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

Answers to POST LAB QUESTIONS AND DATA ANALYSIS

1. Use graphical methods to determine the whole number mole ratio of the two reactants in this

experiment.

The mole ratio is 4 moles OCl to 1 mole S2O32.

2. Why must the total volume of the solution mixture be kept constant in all trials?

The maximum amount of heat was given off when the optimum mole ratio of reactants is combined.
If the solution volume is a constant, the change in temperature will be proportional to the amount of heat
evolved. If the volumes were not constant, a calculation would have to be made relating temperature
change to heat evolved for each separate measurement.

3. The molarities of the reactant solutions were equal in this experiment. Is this necessary, or even
important, for the success of the experiment?

No, it just made it easier! If the molarities were not the same, then a calculation must be performed for
each measurement to relate the temperature change to the heat evolved and the moles of reactant present.

4. Identify the limiting reactant for each trial that you performed.

For Trials 1-4, OCl was the limiting reactant (up to 40 mL OCl added).
For trials 6 & 7, S2O32 was the limiting reactant (less than 10 mL S2O32 added).

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.
Determination of Mass and Mole Relationships in a Chemical Reaction

5. Write the balanced oxidation-reduction reaction for the reaction of OCl and S2O32 in basic solution.
Does the mole ratio that you determined in your experiment match the actual reaction equations
coefficients?

Begin by balancing the redox equation half-reactions in acidic medium, then neutralize any excess H+
ions by adding equal numbers of OH ions to both sides of the balanced reaction:

Reduction: 4 OCl + 2 8 H+ + 2 8 e 4 Cl + 4 H2O

1
Oxidation: S2O32 + 5 H2O 2 SO42 + 10 2 H+ + 8 e

4 OCl + S2O32 + 1 H2O 4 Cl + 2 H+ + 2 SO42

Neutralize H +: 2 OH 2 OH

(2 waters form from neutralization,

one is cancelled, leaving one water)
4 OCl + S2O32 + 2 OH 4 Cl + 2 SO42 + H2O

Yes. The sample data shows that when 40 mL of equimolar NaOCl is mixed with 10 mL of equimolar
NaS2O3, the maximum amount of heat is liberated. Therefore, the optimum mole:mole ratio is 4:1 which
corresponds with the coefficients in the balanced net ionic equation.

6. Suggest a measurement other than the temperature change that could be used in an experiment
involving the method of continuous variations that could be used to determine the mole ratios for a pair
of reactants.

Students should cite observable and measurable quantities such as: color change (measured by
spectrophotometer or colorimeter), mass of precipitate formed (filter, dry ppt. and mass on a balance),
volume of a gas formed (measured by pressure change or gas collection or simply counting bubbles).
Other reasonable answers should also earn credit.

7. Why is it more accurate to use the point of intersection of the two lines to find the mole ratio rather
than the ratio associated with the greatest temperature change?

The exact mole ratio may not have been chosen as a data point. Also, the graph averages several values
to determine the optimum ratio as opposed to relying on a single value.

8. A student mixes two solutions that are not at the same initial temperature. If, 20 mL of Solution A at
23C is mixed with 30 mL of Solution B at 30C, suggest a method for making a correction so that the
student does not have to repeat the experiment.

Initial temperature of mixture =

20.0 mL 23C 30.0 mL 30C
27.2C , So if the measured
50.0 mL
maximum temperature is 35.3C, then T should be reported as (35.3 27.2)C = 8.1C.

Adapted from Advanced Chemistry with Vernier & Laboratory Experiments for Advanced Placement Chemistry by Sally Ann Vonderbrink, Ph. D.