Sei sulla pagina 1di 69

CHEMICAL PRINCIPLES II LAB

Exercise #1: Statistical Treatment of Experimental Data

Objective: To gain experience in the use of statistical analysis of experimental data, and to apply the statistical methods to establish the precision and accuracy of measurements employing laboratory glassware.

Background: Most experiments involve multiple measurements or determinations of the desired result. Usually these repeated trials are performed by one person, but they could also represent a grouping of results from the same experiment performed by several lab workers.

Once the results have been calculated (correctly, we hope!) and tabulated, they must be reported in a manner that represents their reliability to the reader or prospective user of the information. The most common treatment of experimental data uses the science of statistics. What follows is a brief summary of applications from that area. [Anyone majoring in a scientific discipline would benefit greatly from a course in basic statistics.]

Two definitions are important to consider when using scientific data: precision and accuracy. These two words are often used interchangeably in everyday language; however, in scientific work there is a distinct difference between them.

Precision is the proximity of measured results to each other. It is an indication of how reproducibly a result can be determined (i.e., if a procedure is done again and again, will the same answer be attained?).

Accuracy is the comparison of the measured result to the actual or accepted value.

Consider the following examples of quiz grades:

CASE I_

_CASE II_

_CASE III_

 97 % 58 % 97 % 58 % 53 % 99 % 21 % 55 % 98 %
 poor precision good precision good precision poor accuracy poor accuracy good accuracy

Obviously, the desired goal would be to have good precision and good accuracy (as shown in CASE III) for scientific measurements and results.

Let us consider the following results from an experiment to determine the atomic weight (mass) of the element molybdenum (Mo): 97.58, 92.17, 95.36, 90.11, 94.94, and 96.83 g/mole.

The first calculation would involve finding the average (or mean). This is defined as the sum of the individual results (X i ) divided by the number of measurements or results (n):

X
X=
i

n

Let us begin by setting up a data table.

 TRIAL (n) X i 1 97.58 2 92.17 3 95.36 4 90.11 5 94.94 6 96.83 SUM 566.99 X = 94.50

So the average X (pronounced "X bar") will be (566.99 g/mole)/6 = 94.50 g/mole.

Next we will calculate the deviation which is the absolute difference between the

average ( X ) and the individual result (X i ), or |( X - X i )|. By adding deviations and dividing by the number of results, we obtain the average deviation (AD):

| (X-X ) |

i

n

For Trial #1, the deviation would be | 94.50 - 97.58 | = 3.08 g/mole.

 TRIAL (i) X i | X - X i | 1 97.58 3.08 2 92.17 2.33 3 95.36 0.86 4 90.11 4.39 5 94.94 0.44 6 96.83 2.33 SUM 566.99 13.43 X = 94.50 AD=2.24

So the average deviation (AD) will be (13.43)/6 = 2.238333 or 2.24 g/mole. Note each result is given to the hundredth’s place; therefore the mean and average deviation are given to the hundredth’s place.

The relative deviation is defined as the ratio of the average deviation to the mean value. It is often given as a %.

relative deviation =

average deviation

average result

x 100%

In this example, it would be

2 24 g / mol

.

9450

.

g / mol

x 100% =

2.37 %

Here the relative deviation is given with three significant figures. The rubric for multiplication and division is to present results using the least number of significant figures of the factors in the problem.

The relative deviation can also be reported in "parts per thousand", ppt, if the fraction is multiplied by 1000 instead of 100. Here, the answer would be 23.7 ppt. You might also see the relative deviation reported in ppm, "parts per million", which means the fraction is multiplied by 1,000,000 or 10 6 (our answer would be 2.37x10 4 ppm).

The average deviation gives a measure of the precision of the experimental results. In this experiment, we know the accepted or actual result for the atomic mass of Mo. From various books and charts, it is given as 95.94 g/mole. We can therefore report the error of the data. The error is the difference between our average answer and the actual value (often called absolute error). When this is divided by the actual value, we get the relative error. When this is multiplied by 100% we get the percent error.

percent error = | actual value - average experimental result | X 100%

actual value

Using our results:

|(95.94 - 94.50)|

95.94

x 100% = 1.50 % error

We could also report relative error as 15.0 ppt, had we multiplied by 1000 instead of 100. Error and relative errors are measures of accuracy.

Let’s summarize.

Represent a series of data using the average, or mean value - X

Average or percent deviation represents the precision of the data.

Absolute or percent error represents the accuracy of the data.

What happens when we don’t know what the actual, or true value is. After all, isn’t that the goal of doing the measurement to begin with? We have two choices, do the measurement many, many (did I say many) times until we are confident in the result, or rely on statistics to help us estimate the accuracy of our result. In what follows we introduce the statistical approach.

The statistical approach is based on the use of the standard deviation, n-1 (sometimes designated, s). For this, we need to square the individual deviations in the table, obtain the sum, divide by (n-1), and then take the square root of the answer.

standard deviation

n-1 =

(X - X )
2
i
n-1

For Trial #1, the deviation squared would be (3.08) 2 = 9.4864 (g/mole) 2 . We will not worry about the units here, because later when we take the square root, we will end with g/mol again.

With our data, this becomes

405495
.
(
6
 1
)

285

.

g / mol

=

n-1

[You may also see an answer reported with n when the above calculation uses n as the divisor rather than n-1. This is done sometimes if there is a large amount of data so that n n- 1.] The details of the calculation are given in the table below.

 TRIAL (i) X i X - X i ( X - X i ) 2 1 97.58 3.08 9.4864 2 92.17 2.33 5.4289 3 95.36 0.86 0.7396 4 90.11 4.39 19.2721 5 94.94 0.44 0.1936 6 96.83 2.33 5.4289 SUM 566.99 13.43 40.5495 X = 94.50 AD = 2.24  n-l = 2.85

The standard deviation can be reported in terms of relative standard deviation, often using units of % or parts per thousand, ppt:

relative standard deviation = n1

X

or

=

n1

2.85 g / mol

x 100% =

x 1000 =

mol x 100% =

3.02 %

94.50 g / 2.85 g / mol

mol x 1000 = 30.2 ppt

X 94.50 g /

The standard deviation is reported to the same decimal place as the individual results. Here we report the value of n-1 to the hundredth’s place, just as the experimental molar masses. The relative standard deviation is given with three significant figures since this was the least number of significant figures of the factors used in its calculation.

To give an estimate of error of the mean (proximity to the true value), the standard deviation is often converted to an expression called a confidence interval. This is a range,

centered at X , in which we can expect to find the true value with a certain degree of confidence. To determine the confidence interval we make use of the statistical value, t, which can be obtained from the table below.

n-1

t

50%

t

80%

t

90%

t

95%

t

99%

 1 1 3.078 6.314 12.706 63.657 2 0.816 1.886 2.92 4.303 9,925 3 0.765 1.638 2.353 3.182 5.841 4 0.741 1.533 2.132 2.776 4.604 5 0.727 1.476 2.015 2.571 4.032 6 0.718 1.44 1.943 2.447 3.707 7 0.711 1.415 1.895 2.365 3.500 8 0.706 1.397 1.86 2.306 3.355 9 0.703 1.383 1.833 2.256 3.250 10 0.7 1.372 1.812 2.228 3.169 15 0.691 1.341 1.753 2.131 2.947 20 0.687 1.325 1.725 2.086 2.845 ∞ 0.674 1.282 1.645 1.96 2.576

We will calculate a value

(t)(
)
 n  1
n

Using the value of t 90% = 2.015 from the table for n -1 = 5 (n = 6 results), this gives us

(
2 015
.
) (2.85)
 
2 34
.
6

Now we can report our answer as 94.50 ± 2.34 g/mole, meaning that we have a range extending from

the lower confident limit

to the upper confidence limit 94.50 + 2.34 = 96.84 g/mol

94.50 - 2.34 = 92.16 g/mol

This means that there is a 10% chance (100% - 90%) that the true value lies outside the range

92.16 to 96.84 g/mol. The value of 2represents the width of the confidence interval.

The range becomes wider if we want to decrease the odds of misrepresenting the

actual value. Prove to yourself that for 95% confidence, our answer would be expressed as

94.50 ± 2.99 g/mole or that there is a 5% chance of finding the true value outside the range of

91.51 to 97.49 g/mole.

NOTE: If you have a scientific calculator, you will probably notice that you have keys with labels of , 2 , n-1 , n . Thus your calculator is already programmed to do calculations involved in deviations and standard deviations. Because procedures vary amongst different models and manufacturers, you should consult the instruction

booklet that was included with your calculator. [Oh no, where did I put that

]

When performing an experiment, we often have occasion to question a result. Sometimes we know that an error has occurred in the procedure and we make an entry in our notebook to indicate what happened. We might then eliminate that particular trial from our

final calculations with good justification, but we do not obliterate the entry in our records. However, even if a noticeable error has not happened, we might wonder about the validity of a result. For example, notice that the answer for Trial #4 in our data has a high deviation (4.39 g/mole). Should this result be eliminated from our final calculations or must we retain it? There are several statistical ways to evaluate this and one (the Q test) is described below.

First, arrange the results in numerical order (ascending or descending). Working with our data set, we get

97.58

96.83

95.36

94.94

92.17

90.11* (the suspected value that we want to consider)

Take the difference between the highest (97.58) and lowest (90.11) values. This gives us the range of 7.47. Now take the difference between the suspected value (90.11) and its nearest neighbor (92.17). Ignore the sign (+ or -). This gives us 2.06.

Now we define

With our numbers

Q

experimental

=

difference of suspect and nearest neighbor

range

We now consult a statistical table of Q values with different confidence levels depending on the number of results, n (below). For example, with n = 6, Q 50% = 0.560, Q 95% = 0.625, and Q 99% = 0.740.

In our case Q exp = 0.276. This is less than any Q from the table. Thus we are NOT allowed to remove the suspected value of 90.11 from our data. If Q exp > Q from the table, we may eliminate our suspected value. For example, if Q exp = 0.676, we could say that the value 90.11 could be removed from the data with 95% certainty. We would then go back and redo all calculations based on the 5 remaining results.

We finish up this introduction to error analysis by discussing how average deviation, standard deviation and confidence limits relate to the representation of precision and accuracy of experimental results. Measurements can deviate from true results as an accumulation of random and systematic errors. Random errors are equally likely to lead to too high or too low results. By performing a measurement numerous times we can reduce the influence of random errors. We use the confidence interval to indicate the uncertainty resulting from random errors. We use significant figures to represent the limitation of the measurement device. For instruments with digital displays, the precision is given by the right-most digit on the display. (eg. a reading of 9.076 g is precise to +/- 0.001 g). For equipment with graduated scales the precision is taken as +/- 1/10 the smallest division. When representing experimental measurements, the number of digits (significant figures) used should represent the precision of the measurement.

Q-Test values

 N Q 50% Q 95% Q 99% 3 0.941 0.970 0.994 4 0.765 0.829 0.926 5 0.642 0.710 0.821 6 0.560 0.625 0.740 7 0.507 0.568 0.680 8 0.468 0.526 0.634 9 0.437 0.493 0.598 10 0.412 0.466 0.568 15 0.338 0.384 0.475 20 0.300 0.342 0.425 25 0.277 0.317 0.393 30 0.260 0.298 0.372

If we discover that the actual (true) result lies outside the confidence interval it is likely that there are systematic errors at play. Systematic errors will lead to inaccurate results, no matter how many data points are averaged together. Now the confidence interval can help us ferret out potential sources of these errors. As an example, if the true result lies outside a 95% confidence interval, there is a 95% certainty that our technique has introduced a systematic error. One of the main sources of systematic error is the use of an uncalibrated instrument. The following exercises will help you review statistical analysis of data.

 10-11-206, Chemical Principles II Lab Name: Exercise #1 Major:

[1] How many significant figures are indicated in each of the following measurements?

 (a) 0.02670 g significant figures (b) 328.0 mL (c) 7000.0 ng (d) 0.00200cm

[2] A sample containing the known amount of 102 g/L of chloride was analyzed twice by a student. Answers of 101 and 98 g/L were reported by the student.

 (a) Calculate the student's average (mean) answer (b) Calculate the absolute error (c) Calculate the percent error

[3] The weights (masses) of nuclear pellets were found to be 127.2, 128.4, 127.1, 129.0, and 128.1 grams.

 (a) Calculate the average (mean) (b) What is the median (middle measurement)? (c) What is the range of the measurements?

[4] An alloy was analyzed four times for silver and the results were 95.67%, 95.61%, 95.71%, and 95.60% Ag.

 (a) Calculate the standard deviation,  n-1 (b) Calculate the relative standard deviation (in %)

[5] Four measurements of sodium levels in blood samples gave results of 139.2, 139.8, 140.1, and 139.4 mmol/L of Na +

 (a) Calculate the average value (b) Calculate the standard deviation,  n-1 (c) Calculate the relative standard deviation in ppt (d) Calculate the range for 90% confidence (e) Calculate the range for 95% confidence

[6] The precision of a method is being established, and the following data are obtained:

22.23, 22.18, 22.25, 22.09, and 22.17%. Is the 22.09% value a valid measurement at the 95% confidence level? (i.e., should it be included or omitted in the results?)

CIRCLE ONE:

INCLUDE 22.09 or

OMIT 22.09

Lab Exercise 1:

Calibration of a Volumetric Pipet.

Volumetric pipets are used to deliver a specific volume of a liquid. In this exercise you will determine the accuracy and precision of using this tool.

a) Pull the 10-mL volumetric pipet from your drawer.

b) Obtain approximately 100 mL of deionized water in a clean beaker and

allow the temperature to equilibrate with that of the lab.

c) Record the temperature and refer to the density chart posted in the lab to

find the density of water at that temperature.

d) Determine the mass of a dry wash bottle.

e) Discharge 10 mL of deionized water into the wash bottle using the

volumetric pipet. Allow the pipet to drain; don’t force the contents out with the pipet

bulb. Record the mass and determine the volume based on the density of water.

f) Repeat steps (d-e) four more times by adding to the contents of the bottle.

Data:

Temperature of Water:

Density of Water:

Mass of Wash Bottle:

 Trial Mass of Bottle + Water Volume of Pipet 1 2 3 4 5

Average Volume

Average Deviation

Standard Deviation

95% Confidence Interval

1) Does the confidence interval include 10 mL?

Lab Exercise 2:

Precision and Accuracy of a Buret.

Burets are used to deliver a measured volume of a liquid during a titration. In this exercise you will determine experimental accuracy and precision using this tool.

a) Obtain a 50-mL buret

b) Obtain approximately 100 mL of deionized water in a clean beaker and

allow the temperature to equilibrate with that of the lab.

c) Record the temperature and refer to the density chart posted in the lab to

find the density of water at that temperature.

d) Mount the buret to a buret clamp supported by a ring stand.

e) With the stopcock closed, fill the buret to the 0-mark with water. It’s not

important that you fill exactly to the 0-mark, only that you know what the initial reading is. Record this value in the table below.

f) Determine the mass of a clean, dry 150-mL beaker.

g) Discharge ~ 8 mL of deionized water into the beaker from the buret. Try to

get close. You’ll need this skill in week 3 when you perform a titration. Record the

final volume in the buret and the mass of the beaker + water. Calculate the volume discharged using the density of water.

h) Repeat step (g) four more times by adding to the contents of the beaker.

Data:

Temperature of Water:

Density of Water:

Mass of Beaker:

 Trial Mass of Beaker + Water Initial Buret Final Buret Reading Reading 1 2 3 4 5

The volume discharged is simply the final buret reading initial buret reading.

The volume based on mass of water collected is given by V = m/d, where d is the density of water in g/mL.

1) Use these definitions to complete the subsequent data table.

 A B Trial Volume from Volume from mass of H 2 O Percent buret reading Error 1 2 3 4 5
 2) Use column B as the “true” value, determine the percent error for each row. 3) What is the average % error? What is the average absolute error? 4) How does the average absolute error compare to the magnitude of the smallest graduation on the buret? 5) How does the average absolute error compare to the magnitude of the precision of the buret?

Revised: A. Langner 2/22/09

Experiment #2:

Decomposition of KClO 3

Objective: Determine the value of the gas constant, R, by measuring the decomposition of potassium chlorate, KClO 3 , using a liquid displacement method.

Background:

ordinary conditions, that is, at room temperature and atmospheric pressure. Here P is pressure, V is volume, n is moles of gas and T is absolute temperature. The gas constant, R, relates these quantities and is now known to have a value of 0.08206

L.atm/mol.K.

Small deviations from this law are observed, however, because real-

gas molecules are finite in size and exhibit mutual attractive forces. The van der Waals equation,

Most gases obey the ideal-gas equation, PV = nRT, quite well under

 

P

2

n a

V

2

 

V

nb

nRT

eq. 1

where a and b are constants characteristic of a given gas, takes into account these two causes for deviation and is applicable over a much wider range of temperatures and pressures than the ideal-gas equation. The term nb in the expression (V - nb) is a correction for the finite volume of the molecules; the correction to the pressure by the term n 2 a/V 2 takes into account the inter-molecular attractions.

In this experiment you will test the validity of the ideal gas law by determining the gas constant by the thermal decomposition of potassium chlorate, KClO 3 . The evolution of O 2 from the sample can be measured gravimetrically (mass difference) and by measuring the volume of evolved gas by displacement of water. A manganese(IV) oxide, MnO 2 , catalyst will be used to speed up the decomposition reaction. The overall reaction is given by:

2KClO 3 (s) 2KCl(s) + 3O 2 (g)

eq. 2

Analysis of the results will be performed using both the ideal-gas law and the van der Waals equation. The experiment will be performed in triplicate to establish the precision of the measured value.

You will work with mixtures of potassium chlorate and potassium chloride, KCl. From eq. 2 you can see that KCl(s) is a product of the reaction and, consequently, will not react. If a sample of the KClO 3 /KCl mixture is accurately weighed before and after the oxygen has been driven off, the mass of the evolved oxygen can be obtained by difference. From this moles of O 2 can be determined.

The oxygen can be collected by displacing water from a bottle or closed flask, and the volume of gas can be determined from the volume of water displaced. The measurement of displaced water is performed in such a way that the initial and final temperature and pressure are identical. This way the ratio of moles of gas to volume of gas in the closed system must be constant.

Letting n 1 and V 1 represent initial moles and volume of gas (air and water vapor), and n 2 and V 2 by final moles and volume of gas (air, water vapor and evolved O 2 ), we can write the relation;

n

O2

n

2

n

1

V

2

V

1

P

RT

eq. 3

In the case of the van der Waals equation the relationship is a bit more complicated; however, to a good approximation;

n O 2

n

2

n

1

V

2

V

1

RT

 

P

a

  

  V  

 

2

 

n

1

b

V n   

eq. 4

Where n = n 2 -n 1 and V = V 2 -V 1 , respectively. Equations 3 and 4 can be used to determine the gas constant R.

Precautions:

You MUST wear safety goggles at all times while in the laboratoiry.

When sealing the test tube containing the KClO 3 /MnO 2 mixture make sure none of the reactants come in contact with the rubber stopper. KClO 3 is a strong oxidant and will react violently with the stopper if forced into contact with it.

Return unused KClO 3 and MnO 2 in separate vials. Remember, MnO 2 will accelerate the decomposition of potassium chlorate.

Make sure all glassware is secured with clamps before starting the reaction.

Do NOT remove hoses from the glass tubing.

Replace the cap on the syringe needle after use.

All usual safety precautions should be followed, including any special precautions given by your instructor.

Procedure:

Work in partners

1.

Obtain a vial of potassium chlorate (KClO 3 ) and a vial of manganese(IV) oxide (MnO 2 ). Both reactants have been mixed with inert potassium chloride (KCl).

2. Assemble the experimental apparatus shown in Figure 1, but don’t attach the test tube. The tubes and stoppers have already been pre-assembled. You will use a 250-mL Aspirator Flask rather than a bottle. The aspirator flask should be clamped to a ring stand to secure it. Fill the flask with water to the neck. Fill glass tube A and the rubber tubing with water by loosening the pinch clamp and attaching a rubber bulb to the end of tube B and applying pressure through it. Close the clamp when the tube is filled.

3. Add approximately 0.20 g of the MnO 2 /KCl mix and 0.5 g of KClO 3 to the provided test tube. Accurately determine the mass of the test tube and contents to the nearest 0.0001 g. Mix the solids in the test tube by rotating the tube, being certain that none of the mixture is lost from the tube. Cover the tube with the rubber septa. Clamp the tube to a ring stand and attach tube B by pushing the needle through the septa. (CAUTION: When you attach the test tube, be certain that none of the solid mixture contacts the septa. With added heat and pressure a violent reaction could result.)

Figure 1: Experimental Apparatus

4. Fill the beaker about half full of water, insert the end of tube A in it, open the pinch clamp, and lift the beaker until the levels of water in the flask and beaker are identical. Then close the clamp, discard the water in the beaker, dry the beaker, and determine it’s mass. The purpose of equalizing the levels is to produce atmospheric pressure inside the flask and test tube.

5. Set the beaker with tube A in it on the bench and open the pinch clamp. A little water will flow into the beaker, but if the system is airtight and has no leaks, the flow will soon stop and tube A will remain filled with water. If this is not the case, check the apparatus for leaks and start over. Leave the small amount of water in beaker, at the end of the experiment, the water levels will be adjusted and this water will flow back into the bottle.

6. Heat the lower part of the test tube gently (be certain that the pinch clamp is open) so that a slow but steady stream of gas is produced, as evidenced by the flow of water into the beaker. When the rate of gas evolution slows considerably, increase the rate of heating, and heat until no more oxygen is evolved. Allow the apparatus to cool to room temperature, making certain that the end of the tube in the beaker is always below the surface of the water. Equalize the water levels in the beaker and the bottle as before and close the clamp.

7. Determine the mass of the beaker with water. Measure the temperature of the water and, using the density of water in Table 1, calculate the volume of the water displaced. This is equal to the volume of oxygen produced.

8. Remove the test tube from the apparatus and accurately weigh the tube plus the contents. The difference in mass between this and the original mass of the tube plus solids is the mass of the oxygen produced.

10. Repeat the experiment 2 more times for a total of three trials using a new test tube for each trial.

Waste Disposal Instructions KClO 3 is a powerful oxidizing agent and should not be disposed of in a waste basket! Do not attempt to clean out the residue that remains in the test tube. Return the test tube to the instructor or follow his instructions for disposal of its contents.

TABLE 1 Density and Vapor Pressure of Pure Water at Various Temperatures

Temperature

o

C

Density

g/mL

Temperature

o

C

Vapor Pressure

mmHg

 15 0.999099 15 12.8 16 0.998943 16 13.6 17 0.998774 17 14.5 18 0.998595 18 15.5 19 0.998405 19 16.5
 20 0.998203 20 17.5 21 0.997992 21 18.6 22 0.997770 22 19.8 23 0.997538 23 21.1 24 0.997296 24 22.4 25 0.997044 25 23.8 26 0.996783 27 0.996512 28 0.996232 Data & Analysis Table 2: Moles of O 2 Evolved. Trial 1 Trial 2 Trial 3 Mass of test tube + reactants (g) Mass of test tube + products (g) Mass of O 2 evolved (g) Moles of O 2 evolved (mole) Table 3: Volume of Water Displaced Trial 1 Trial 2 Trial 3 Mass of dry beaker (g) Mass of beaker + water (g) Mass of water displaced (g) Temperature of water ( o C) Density of water (g/mL) Volume of water displaced, V 2 -V 1 (L) Table 4: Determination of Gas Constant (For eq. 4 use a = 1.360 L 2 atm/mol 2 , b =

31.83 cm 3 /mol)

R from eq. 3

R from eq. 4

Trial 1

 Trial 2 Trial 3 Average, X Standard Deviation,  n-1 95 % Conf. Int., X ±  Questions:

1. Does your value of R based on the ideal gas law agree with the accepted value within

the confidence limits of the result?

2. Does your value of R based on the van der Waals equation agree with the accepted

value within the confidence limits of the result?

3. How does the solubility of oxygen in water affect the value of R you determined?

4. Use the van der Waals equation to calculate the pressure exerted by 1.000 mol of Cl 2 ;

in 22.41 L at 0.0 °C. The van der Waals constants for Cl 2 ; are: a = 6.49 L 2 atm/mol 2 and b = 0.0562 L/mol.

5. How much potassium chlorate is needed to produce 20.0 mL of oxygen gas at 670

mm Hg and 20°C?

6. A certain compound containing only carbon and hydrogen was found to have a vapor density of 2.550 g/L at 100°C and 760 mm Hg. If the empirical formula of this compound is CH, what is the molecular formula of this compound?

Experiment #3: Acid-Base Titrations

Objective: Determine the concentration of acid in an aqueous unkown by using the technique of acid-base titration with an indicator.

Background: There are many definitions or classifications of acids and bases. For this experiment, the Arrhenius definitions will be most useful:

An acid is a substance that provides hydrogen ions (H + ) in aqueous solution. A base is a substance that provides hydroxide ions (OH - ) in aqueous solution. Neutralization is the reaction of the H + from the acid with the OH - of the base:

HX(aq) + MOH(aq)

MX(aq) + H 2 O(l)

eq. 1

Here X - is a monovalent anion (e.g. Cl - ) and M + is a monovalent cation (e.g. Na + ). The product of a neutralization reaction is a salt and water.

Using compounds as examples of acids and bases, we get equations such as these:

H + Cl -

+ Na + OH -

K + H + C 8 H 4 O 4 2- + Na + OH -

Acid

Base

Na + Cl -

+

H 2 O

K + Na + C 8 H 4 O 4 2- + H 2 O

salt

water

eq. 2

eq. 3

Equation 2 represents the reaction between hydrochloric acid and sodium hydroxide to produce sodium chloride and water. Equation 3 appears more complicated, but it still represents an acid, potassium hydrogen phthalate (KHP) reacting with a base, sodium hydroxide (Na + OH - ) to produce a salt, potassium sodium phthalate (K + Na + C 8 H 4 O 4 2- ) and water. The molecular structure of the phthalate anion is given below.

O
O
-O
O-

Notice that both reactions 2 and 3 involve reacting one mole of acid with one mole of base; some reactions have ratios that are not one-to-one. When the reaction is complete, this is called the equivalence point. All of the acid will have reacted with all of the base and the flask or beaker will now contain only the salt produced with water.

Often a visual method is used to determine when the reaction is completed. We will use an acid-base indicator that changes color dramatically as the solution changes from acidic to slightly basic (or vice versa). The indicator will be phenolphthalein, often abbreviated as "phth" It is colorless in acid and pink in base. When the indicator changes color, this is called the end point of the reaction and the indicator is selected so that the end point and the

equivalence point will be close, consequently giving results.

Titration is a technique that involves a controlled reaction between two substances. In our experiment, one substance (the base, NaOH) is placed in a buret and the other substance (the acid, KHP) is in a flask. The phenolphthalein indicator is added to the flask containing the acid, then NaOH is slowly added to this mixture until the indicator changes from colorless to pink. This signals the end of the reaction.

We will first make a dilute solution of NaOH from a more concentrated solution (often called a stock solution). The concentration of the dilute NaOH solution will be determined by titrating it using a known amount of acid (KHP). Through this procedure the NaOH solution is standardized. Now that the concentration (molarity) of the NaOH is known, it can be used to determine the amount of acid in any appropriate sample, such as acid rain, stomach fluid, urine, soda, or a laboratory unknown.

PRECAUTIONS:

* You MUST wear safety goggles at all times while in the laboratory.

* Although the acids and bases we will use are rather dilute,

- wash your hands well if acid or base gets on them

- you may wish to wear gloves

- you may wish to wear an apron or lab coat

- wash your lab bench well to remove any acid or base spills

* All solutions may be rinsed into the sinks with running tap water.

* Pipets should be used only with bulbs or pumps. NO pipeting by mouth!

* All normal safety rules must be obeyed, including any special precautions issued by your instructor.

Procedure: (work in pairs)

1. PREPARATION of NaOH SOLUTION and the BURET

The preparation of the NaOH titrant solution should be done by one lab partner.

A. Using a 50- or 100-mL graduated cylinder, measure 250 mL of distilled water into a 500-mL flask. With a 10-mL graduated cylinder, obtain 10 mL of 6 M NaOH and add it to the flask. Mix very well. Pour into a plastic or glass storage bottle and cap the bottle (or leave in flask and cover with plastic film). Label this solution as "NaOH titrant" and set aside. Make sure the valve to the carboy containing the 6 M NaOH(aq) is closed after use.

Determination 1: Calculate the approximate molarity of the "NaOH titrant" solution and record it in the data table. (This is a dilution problem so use M 1 V 1 = M 2 V 2 where M represents molarity and V is volume.)

B. Obtain a 50-mL buret. Clean with soapy water and rinse several times with tap water, then rinse with distilled water 2 or 3 times. Pour some of the "NaOH titrant" into a small beaker and rinse the buret with 2 or 3 small (5-10 mL) portions of it. The buret does not have to be dry, but now any liquid in the buret is the "NaOH titrant".

C. Set up a ring stand with the buret clamp. Attach the buret and, using the small buret funnel, slowly pour "NaOH titrant" solution into the buret, filling it to above the zero-line. Place a "waste beaker" below the buret and allow some solution to run out, making sure that the buret tip is filled and has no air bubbles. Adjust the level of the liquid in the buret to between 0 and 5 mL. It DOES NOT have to be at 0.00 mL to begin!

II PREPARATION of KHP SAMPLE

The preparation of the KHP solution should be done by one lab partner.

A. Clean five 125- or 250-mL flasks. Rinse with distilled water. They do not need to

be dry. With a wax pencil, label them as A, B, C, D, E or 1, 2, 3, 4, 5 or any way you

wish.

B. Using a plastic weighing boat, measure approximately 0.6 grams of KHP

(potassium hydrogen phthalate). The amount doesn't have to be exactly 0.6 grams, but you need to know and record exactly what amount you have (i.e., 0.5832 g or 0.6117 g) in the data table. Add the weighed KHP to the first flask and using the squirt bottle, rinse the plastic weighing boat with distilled water allowing the liquid to go into the

 flask. C. Repeat this process for the other four flasks. D. Using the 50- or 100-mL graduated cylinder, measure and add 30 mL of distilled

water to each flask. Swirl to dissolve the KHP solid.

Determination 2: Calculate the moles of KHP you have and enter it in your data table.

Example: Suppose you weighed 0.6117 grams of KHP.

= 0.002995 moles KHP

0.6117 g KHP x

1 mole KHP 204.23 g KHP

III. STANDARDIZATION of NaOH TITRANT

A. Record the initial reading of the "NaOH titrant" in the buret, using a card with a

chart.

B. Place a piece of white paper on the base of the ring stand. Add 3 or 4 drops of

phenolphthalein to the first flask of KHP solution. Slowly add "NaOH titrant" while constantly swirling the flask to mix. Have your instructor show you. You will see some pink that disappears quickly, but as you continue to add NaOH, the pink will stay

longer. Slow down and start adding very small amounts until the pink color persists when swirled. You are aiming for the lightest pink possible. Read and record the final volume of "NaOH titrant" from the buret. [After the sample sits for a few minutes, the color may disappear, but that is OK.]

C. Refill the buret. Repeat the procedure for the next flask until all five have been

titrated. Dispose of the waste in the sink with running tap water. Leave the buret ready for the next part.

Determination 3: What is the molarity of the "NaOH titrant" obtained from each titration? Enter this in the data table.

Example: The titration required 14.65 mL of NaOH for the sample from Part II which contained 0.002995 moles KHP.

0.002995 moles KHP x 1 mole NaOH = 0.2044 M NaOH

0.01465 L NaOH sol'n

1 mole KHP

Is the molarity of the NaOH solution close to your estimate from Part IA? [If it seems really different from your estimate or prediction, check for potential errors.]

Determination 4: Calculate the average molarity of the NaOH titrant solution, the standard deviation, and the 95% confidence interval. Include this in your report.

IV. CONCENTRATION of UNKNOWN ACID SAMPLE

 A. Obtain an unknown from your instructor and record its number NOW! B. Using a pipet bulb or pipet pump and your 10-mL volumetric pipet, transfer 10- mL of unknown to a clean 125- or 250-mL flask. Add 20 mL of distilled water, using the graduated cylinder. Add 3 or 4 drops of phenolphthalein. Record the initial

volume of NaOH in the buret and titrate until the color becomes a persistent light pink. Record the final volume in the buret. Refill the buret with NaOH titrant solution

and repeat the procedure for a total of 5 trials.

After you finished the first titration, you should be able to predict how many mL the second sample should require. For subsequent trials add about 2/3 of that very quickly, then slow down to reach the end point.

Determination 5: What is the molarity of the acid in the original unknown?

Example: 10-mL of unknown required 22.50 mL of 0.2044 M NaOH to reach the end point. Be sure to use average molarity of NaOH from Part III.

22.50 mL NaOH sol'n x 0.2044 moles NaOH x 1 mole unk acid = 0.4599 M

1 L NaOH sol'n

Determination 6: Calculate the average molarity of the unknown acid solution, the standard deviation, and the 95% confidence interval. Include this in your report.

10.00 mLunk acid

1 mole NaOH

unk acid

V. CLEAN-UP

A. All solutions, including the NaOH, can be washed down the drain with running tap water.

B. Return the KHP vial and unknown container to the instructor.

C. Clean your equipment and lab bench area.

VI. DETERMINATIONS & DATA TABLES

PART III: STANDARDIZATION of NaOH TITRANT

Determination 1: Approximate Molarity of NaOH Titrant

Table 1: Molarity of NaOH Titrant (Determination 2 & 3)

mL NaOH
mL NaOH
mL NaOH
TRIAL
g KHP
moles
Final
initial
Used
M NaOH
KHP

Determination 4:

Average Molarity of NaOH

Standard Deviation

95% Confidence Interval

PART IV: DETERMINATION of UNKNOWN ACID MOLARITY

Table 2: Molarity of Acid Unknown (Determination 5)

 Unk# mL NaOH mL NaOH mL NaOH M of Acid TRIAL final Initial used Unknown

Determination 6:

Average Molarity of Acid

Standard Deviation

95% Confidence Interval

Questions:

Question 1: Suppose in step II-D you unknowingly added 35 mL of distilled water to

one of the five flasks instead of 30 mL. Does this lead to a systematic error in your results? Why or why not?

Question 2: Suppose in procedure IV you and your lab partner got your signals crossed and you both added 20 mL of distilled water to one of the flasks containing 10-

mL of unknown. Does this lead to a systematic error in your results? Why or why not?

Question 3: When phenolphthalein is used as an indicator the pink color at the end point of a titration tends to fade over time. What does this indicate about changes in the solution? Give a possible explanation for this change.

Question 4: Potassium hydrogen phthalate is a monoprotic acid. dihydrogen phthalate (H 2 C 8 H 4 O 4 ) is a diprotic acid. An analyte sample contains 0.127 M KHP and 0.0678 M H 2 C 8 H 4 O 4 . What volume of a 0.205 M NaOH solution is required to neutralize 25.0

mL of the analyte solution? Show your work.

Revised: A. Langner 3-21-2009

Experiment #4:

Heat of Neutralization

Objective: To measure, using a calorimeter, the energy changes accompanying neutralization reactions.

Background:

usually in the form of heat. The energy change of a reaction that occurs at constant pressure is termed the heat of reaction or the enthalpy change. The symbol H = H final - H initial is used to denote the enthalpy change. If heat is evolved, the reaction is

exothermic (H < 0); and if heat is absorbed, the reaction is endothermic (H > 0). In this experiment, you will measure the heat of neutralization (or the enthalpy of neutralization) when an acid and a base react to form water and a soluble salt.

Every chemical change is accompanied by a change in energy,

This quantity of heat is measured experimentally by allowing the reaction to take place in a thermally insulated vessel called a calorimeter. The heat liberated in the neutralization will cause an increase in the temperature of the solution and of the calorimeter. If the calorimeter were perfect, no heat would be radiated to the laboratory. The calorimeter you will use in this experiment is constructed from styrofoam coffee cups covered by a plastic lid. Some heat will be lost through the top; therefore, the calorimeter will have to be calibrated.

Calibration of the calorimeter involves determining its heat capacity, C cal . By "heat capacity of the calorimeter" we mean the amount of heat (that is, the number of joules) required to raise its temperature 1 Kelvin, which is the same as 1°C. Provided the calibration is done in the temperature range encountered during the neutralization reaction, C cal incorporates both the heating up of the cups themselves and the heat loss through the plastic top. Once calibrated, the calorimeter can be used to determine the enthalpy change of a reaction. At constant pressure the heat released by a reaction is equal to H rxn for the reaction. The released heat of reaction is absorbed by the calorimeter contents, the calorimeter and is lost through the top. Mathematically we write

q released = -H rxn = mC s T + C cal T

eq. 1

Here m and C s are the mass and specific heat capacity of the reaction solution. The temperature change T = T f T i (final initial).

The heat capacity of the calorimeter is determined by measuring the tem- perature change that occurs when a known amount of hot water is added to a known amount of cold water in the calorimeter. The heat lost by the warm water is equal to

the heat gained by the cold water and the heat absorbed by the calorimeter. For example, if T 1 equals the temperature of 50 mL of cold water and the calorimeter, T 2 equals the temperature of 50 mL of warm water added to it, and T f equals the temperature after mixing, then the heat lost by the warm water is

heat lost by warm water = (T 2 - T f ) x 50 g x 4.18 J/g o C

eq. 2

The specific heat of water is 4.18 J/K-g, and the density of water is 1.00 g/mL. The heat gained by the cold water is

heat gained by cold water = (T f T 1 ) x 50 g x 4.18 J/g o C

eq. 3

The heat lost to the calorimeter is the difference between heat lost by the warm water and that gained by the cold water:

(heat lost by warm water) (heat gained by cold water) =

Substituting equations 2 and 3 we have

heat gained by the calorimeter

[(T 2 - T f ) x 50 g x 4.18J/g o C] - [{T f T 1 ) x 50 g x 4.18J/g o C]

= C cal x (T f T 1 )

eq. 4

Note that the heat lost to the calorimeter equals its temperature change times its heat capacity. Thus by measuring T 1 , T 2 , and T f , the heat capacity of the calorimeter can be calculated from equation 4. The following example illustrates this procedure.

Example 1

Given the following data, calculate the heat lost by the warm water, the heat gained by the cold water, the heat lost to the calorimeter, and the heat capacity of the calorimeter:

Temperature of 50.0 mL warm water: 37.92°C = T 2

Temperature of 50.0 mL cold water: 20.91 °C = T 1

Temperature after mixing: 29.11 °C = T f

SOLUTION: The heat lost by the warm water, where T = 37.92 °C - 29.11 °C, is

8.81 K x 50 g x 4.18 J/g o C = 1840 J

The heat gained by the cold water, where T = 29.11 °C - 20.91 °C, is

8.20 K x 50 g x 4.18J/g o C = 1710 J

The heat gained by the calorimeter is

1840 J - 1710 J = 130 J

The heat capacity of the calorimeter is, therefore,

130J/8.20K = 16.0 J/K

Once the heat capacity of the calorimeter is determined. equation 1 can be used to determine the H for the neutralization reaction. Example 2 illustrates such a calculation.

Example 2

Given the following data, calculate the heat gained by the solution, the heat gained by the calorimeter, and the heat of reaction:

Temperature of 50.0 mL of acid before mixing: T i = 21.02 °C Temperature of 50.0 mL of base before mixing: T i = 21.02 °C Temperature of 100.0 mL of solution after mixing: T f = 27.53 °C

SOLUTION: The heat gained by the solution, where T = 27.53 °C - 21.02 °C, is

6.51 K x 100 g x 4.18 J/K-g = 2720 J

The heat gained by the calorimeter, where T - 27.53 °C - 21.02 °C, is

6.51 K x 16.0 J/K = 104 J

The heat of reaction is therefore

2720 J + 104 J = 2824 J = 2.82 kJ

Precautions:

You MUST wear safety goggles at all times while in the laboratory.

Although the acids and bases used are dilute,

-- wash your hands well if acid or base gets on them

 -- don’t get solutions in your eyes or on your clothes -- you may wear gloves and/or a lab apron

-- clean acid or base spills with ample water

All solutions may be rinsed into the sinks with running water.

All usual safety precautions should be followed, including any special precautions given by your instructor.

Procedure:

A. Heat Capacity of Calorimeter

1) Construct a calorimeter similar to the one shown in Figure1 by nesting two Styrofoam cups together. Make a hole in the lid just big enough to admit the thermometer. Place the cups in a 400-mL beaker to provide stability. Using a clamp support the thermometer in the calorimeter, making sure the thermometer bulb doesn’t touch the bottom of the inner cup. To protect the thermometer, wrap some paper towels around the top as you gently clamp down.

Work in partners

2) Place exactly 50.0 mL of tap water in the calorimeter cup and replace the cover and thermometer. Allow 5 to 10 min for the system to reach thermal equilibrium; then record the temperature to the nearest 0.1 °C on the report sheet.

Clamp

Thermometer

Lid

Styrofoam

Cu

s

Figure 1: Schematic of Calorimeter

3) Place exactly 50.0 mL of water in a clean, dry 250-mL beaker and heat the water on a hot plate until the temperature is approximately 15° to 20°C above room temperature. Do not heat to boiling, or appreciable water will be lost, leading to an erroneous result. Allow the heated water to stand for a minute or two, recording the temperature to the nearest 0.1 o C as you wait. The largest error in the lab occurs when the thermometer hasn’t had the chance to reach the same temperature as the hot water, so be patient.

4) Immediately after taking a temperature measurement of the warm water pour it as completely as possible into the calorimeter, making sure the contents are thoroughly mixed. Replace the lid and the thermometer, then observe the temperature for the next 3 min and record the temperature every 15 s on the

temperature vs. time data sheet.

5) Determine T by taking the difference between the maximum temperature on your data sheet and the initial temperature of the cold water.

6) Repeat Steps 2-4 two more times, interchanging the inner and outer calorimeter cup each time. Be sure the cups are thoroughly dried between uses.

B. Heat of Neutralization of HCl( aq) + NaOH(aq) H 2 O(l ) + NaCl( aq)

1) Dry the calorimeter and the thermometer with a towel. Carefully measure 50.0 mL of 1.0 M NaOH and add it to the calorimeter. Place the lid on the calorimeter but leave the thermometer out.

2) Measure out exactly 50.0 mL of 1.0 M HCl into a dry beaker. Allow it to stand near the calorimeter for 3 to 4 min. Measure the temperature of the acid, rinse the thermometer with tap water, and wipe dry.

3) Insert the thermometer into the calorimeter and measure the temperature of the NaOH solution. The temperatures of the NaOH and the HCl should not differ by more than 0.5°C. If the difference is greater than 0.5°C, adjust the temperature of the HCl by either warming it by holding the beaker in your hands or cooling the out- side of the beaker with tap water until the temperature of the HCl is within 0.5 °C of that of the NaOH, then record the temperature of both solutions in your data table.

4) Lift the lid of the calorimeter and carefully add the 1.0 M HC1 all at once. Be careful not to splash any on the upper sides of the cup. Make sure the contents are thoroughly mixed then replace the lid and thermometer of the calorimeter.

5) Record the temperature as a function of time every 15 s for the next 3 min.

6) Determine T by using the highest temperature in your data table. Calculate the heat of neutralization per mole of water formed. You may assume that the NaCl solution has the same density and specific heat as water.

7) Repeat Steps 1-6 two more times, interchanging the inner and outer calorimeter cup each time. Be sure the cups are thoroughly dried between uses and the thermometer is rinsed with water.

C. Heat of Neutralization of HC 2 H 3 O 2 (aq) + NaOH(aq) H 2 O(l ) + NaC 2 H 3 O 2 (aq)

Follow the same procedure as in Part B, but substitute 1.0 M HC 2 H 3 O 2 for 1.0 M HCl. Calculate the heat of neutralization per mole of water formed.

Waste Disposal Instructions Handle the stock solutions carefully. You may use a wet sponge or paper towel to clean up any spills. The reaction mixtures produced in the Styrofoam cups contain harmless salts. They can be discarded in the sink with running water. Do not discard the Styrofoam cups. They should be returned to your instructor.

Data & Analysis:

A. Heat Capacity of Calorimeter

Table 1: Temperature vs. Time Data for Calorimeter Calibration

Trial 1
Temp., o C
Trial 2
Temp., o C
Trial 3
Temp., o C
Calorimeter &
Cool Water, T 1
Warm Water,
T
2
Combined
Time (s)
0
15
30
45
60
75
90
105
120
135
150
165
180
Table 2: Heat Capacity of Calorimeter. (see example 1)
Trial 1
Trial 2
Trial 3
Final Temperature, T f
Heat lost by warm water (J)
Heat gained by cool water (J)
Heat absorbed by calorimeter (J)
Calorimeter heat capacity, C cal in
J/ o C

Average value of C cal

Standard Deviation of C cal

of C cal at 95% confidence

B. Heat of Neutralization for HCl(aq) + NaOH(aq) H 2 O(l ) + NaCl( aq)

Table 3: Temperature vs. Time Data for HCl NaOH Neutralization

Trial 1 Temp., o C

Trial 2 Temp., o C

Trial 3 Temp., o C

Initial Temp of NaOH(aq), T i Initial Temp of HCl(aq)

Time (s)

0

15

30

45

60

75

90

105

120

135

150

165

180

Combined

Table 4: Molar Heat of Neutralization for HCl - NaOH. (see example 2)

 Trial 1 Trial 2 Trial 3 T for reaction from data Heat gained by solution (J) Heat absorbed by calorimeter (J) Total heat released by reaction (J) Moles of water produced (moles) Molar heat of reaction, H rxn in kJ

Average value of H rxn

Standard Deviation of H rxn

of H rxn at 95% confidence

C. Heat of Neutralization of HC 2 H 3 O 2 (aq) + NaOH(aq) H 2 O(l ) + NaC 2 H 3 O 2 (aq)

Table 5: Temperature vs. Time Data for HC 2 H 3 O 2 - NaOH Neutralization

Trial 1 Temp., o C

Trial 2 Temp., o C

Trial 3 Temp., o C

Initial Temp of NaOH(aq), T i Initial Temp of HCl(aq)

Time (s)

0

15

30

45

60

75

90

105

120

135

150

165

180

Combined

Table 6: Molar Heat of Neutralization for HC 2 H 3 O 2 - NaOH. (see example 2)

 Trial 1 Trial 2 Trial 3 T for reaction from data Heat gained by solution (J) Heat absorbed by calorimeter (J) Total heat released by reaction (J) Moles of water produced (moles) Molar heat of reaction, H rxn in kJ

Average value of H rxn

Standard Deviation of H rxn

of H rxn at 95% confidence

Questions:

1. The accepted value for the molar enthalpy of neutralization is H o = -55.81 kJ/mol. {P.J. Cerutti et al., Can. J. Chem. 56 (1978) 3084 ) Does this result fall within

the confidence limits of your experimental value for the HCl NaOH neutralization reaction? If not, give sources of error that may explain the discrepancy.

2. Answer question 1 using your HC 2 H 3 O 2 NaOH results. Why would the value of

H o be the same for the two reactions?

3. The experimental procedure has you wash your thermometer and dry it after you

measure the temperature of the NaOH solution and before you measure the temperature of the acid solution. Why?

4. Describe how you could determine the specific heat capacity of a metal by using

the apparatus and techniques in this experiment.

5. When a 3.25-g sample of solid sodium hydroxide was dissolved in a calorimeter

in 100.0 g of water, the temperature rose from 23.9 °C to 32.0°C. Calculate H (in kJ/mol) for the solution process:

NaOH(s) Na + (aq) + OH - {aq)

Use a calorimeter heat capacity of C cal = 15.8 J/ o C.

6. A 50.0-mL sample of a 1.00 M solution of CuSO 4 is mixed with 50.0 mL of 2.00 M

KOH in a calorimeter. The temperature of both solutions was 20.2°C before mixing and 26.3°C after mixing. The heat capacity of the calorimeter is 12.1 J/K. From these

data calculate H for the process

CuSO 4 (l M) + 2KOH(2 M) Cu(OH) 2 (s) + K 2 SO 4 (0.5 M)

Experiment #5: Kinetics I - The Rate Equation Reaction between Oxalic Acid and Potassium Permanganate

Objective: Determine the rate law for the reaction of oxalic acid with potassium permanganate using a colorimetric analysis.

Background: Chemical reactions occur at various rates. Some occur instantaneously when the reactants are mixed using optimum conditions - explosions are an example of this kind of reaction. Others require a long time to occur - rusting of iron on a car is a slow process. In industry, controlling the rate of a reaction is of prime importance; it can often influence the purity of a product, its final form (i.e., big clumps or small particles), and several other characteristics. Conditions that commonly play a role in the rate of a reaction are concentration of the reactants, pressure (especially if gaseous reactants are involved), temperature, and the presence of a catalysts. In this experiment we will consider the importance of concentration of oxalic acid and of potassium permanganate in determining the overall rate of reaction between them. The rate is an experimentally determined quantity. Most reactions occur through a series of steps called a reaction mechanism. More often than not, the mechanism is not known. Consequently the observed rate cannot be predicted from the stoichiometry of the reaction. For right now, we will simply write that

KMnO 4 (aq) + H 2 C 2 O 4 (aq) Intermediate products

purple colorless

red

pale yellowish

We can observe the progress of this reaction by its color. When the reactants are mixed, we will see the dark purple color of potassium permanganate change to a red reaction intermediate, which gradually changes over to a pale yellow product solution. By measuring the time from mixing to the appearance of the red intermediate, we can obtain the rate of reaction. The rate of a reaction is a measure of the change in concentration of reactants and products with time. Like the speed of a car, a rate is always a positive number. Therefore, the rate based on the potassium permanganate concentration would be written:

[KMnO ]

4

t

= rate

eq. 1

Here [KMnO 4 ] represents the change in potassium permanganate concentration during the time interval t. Since the concentration decreases, the minus sign is needed to make the rate come out positive. The rate law expression gives the dependence of the reaction rate on the concentration of reactants. For the reaction under investigation, we write the rate law as

rate = k[KMnO 4 ] X [H 2 C 2 O 4 ] Y

eq. 2

where the [ ] indicates molarity (moles/L), and X and Y are called the orders with respect to potassium permanganate (X) and oxalic acid (Y), respectively. The values of X and Y are not always integers; they are often fractions or decimal numbers. The overall rate order would be "X + Y". Finally the constant, k, is called the rate constant for the reaction and it is a constant at any one temperature. Suppose we do two experiments, keeping the potassium permanganate concentration constant for both, [KMnO 4 l 1 , but varying the oxalic acid concentration,

[H 2 C 2 O 4 ] 1 and [H 2 C 2 O 4 ] 2 . We could write two rate expressions now:

 Experiment #1: rate 1 = k[KMnO 4 ] 1 x [H 2 C 2 O 4 ] 1 y Experiment #2: rate 2 = k[KMnO 4 ] 1 x [H 2 C 2 O 4 ] 2 y

If we now take the ratio of these two experimental results

rate

rate

 k[KMnO ] 4 X [H C O 2 2 4 ] 1 Y X 2 Y 1 2 2 4

1 1

=

2 k[KMnO4] [H C O ]

By cancelling k [KMnO 4 ] 1 X , we would get

rate

1

rate

2

=

Y

1

[H C O [H C O

2

2

4

]

4

]

Y

2

2

2

eq. 3

If we now take the natural (or Naperian) logarithm of both sides of eq. 3 we would get

  

 rate rate 1 2    = Yln    [H C O 2 2 [H C O 2 2 4 4 ] 1    ] 2  ln rate /rate 1 2   [H C O ] /[H C O ] 2 2 4 1 2 2 4 2 

ln

We could now solve for Y.

Y= ln

eq. 4

By reversing the process (varying the concentration of KMnO 4 and keeping the concentration of H 2 C 2 O 4 constant), we can find the value of X. Then we can solve for the overall rate order, X + Y. The rate constant, k, can be determined by substituting X and Y into the rate expression eq. 2.

Precautions:

You MUST wear safety goggles at all times while in the laboratory.

● KMnO 4 (potassium permanganate) stains skin and clothes, the purple color

changes to dark brown. It will wear off the skin with normal washing, but will cause a permanent stain on clothing.

- you may wish to wear gloves and an apron or lab coat

It is always a good idea to

- wash your hands well if in contact with chemicals

- wash your tab bench well to remove any spills

All solutions should be placed in the special containers in the hoods.

Pipets should be used only with bulbs or pumps. NO pipeting by mouth!

All normal safety rules must be obeyed, including any special precautions issued by your instructor.

Procedure: (work in pairs)

A. Using clean beakers and a graduated cylinder, obtain the following:

● 80 mL of distilled water in a 150- or 200- or 250- mL beaker

● 25 mL of 0.130 M KMnO 4 in a small (50- or 100-mL) beaker

● 120 mL of 0.755 M H 2 C 2 O 4 in a 200- or 250-mL beaker

● One sealed tube (vile) of Eriochrome Black T solution.

Record the temperature in the lab in °C These solutions will be used to prepare the concentration series for the experiments. A table of the solution combinations is given below. The subsequent procedure describes how the solutions are to be mixed.

Table 1: Solution Volumes for Three Experimental

 Reactants Experiment #1 Experiment #2 Experiment #3 distilled water 6,00 mL 1.00 mL 5.00 mL 0.130M KMnO 4 1.00 mL 1.00 mL 2.00 mL 0.755 M H 2 C 2 O 4 5.00 mL 10.00 mL 5.00 mL Total Volume 12.00 mL 12.00 mL 12.00 mL [KMnO 4 ], M [H 2 C 2 O 4 ], M

Determination #1: Calculate the molarity of KMnO 4 and H 2 C 2 O 4 for each set-up.

Example: Experiment #1

(0.130 M KMnO )(1.00 mL KMnO

4

4

) = 0.0108 M

12.00 mL solution

Use a similar approach for the oxalic acid concentration.

B. Using disposable pipets, measure 6.00 mL of distilled water and 5.00 mL of oxalic acid

into a test tube and stir well with a glass stirring rod.

C. One partner should measure 1.00 mL of potassium permanganate and prepare to add it to

the test tube. The other partner should be ready to start the timer when the permanganate is added. Stir immediately. The solution will change color from purple to red to yellow. Record the time when the solution color matches that of the tube of Eriochrome Black T.

and dry the test tube. Repeat steps (B) and (C), rotating duties of the partners, for a total of 5 trials.

E. Repeat the procedure for the amounts in Experiment #2 and then for the amounts in

Experiment #3.

Data and Calculations

Table 2: Data for Experiment #1 Conditions

T =

o C

 [KMnO 4 ] [H2C 2 O 4 ] time (s) Rate 1 = [KMnO 4 ]/time Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Average Rate Standard dev. 95% conf., 

Table 3: Data for Experiment #2 Conditions

T =

o C

 [KMnO 4 ] [H2C 2 O 4 ] time (s) Rate 2 = [KMnO 4 ]/time Trial 1 Trial 2 Trial 3 Trial 4 Trial 5 Average Rate Standard dev. 95% conf., 

Table 4: Data for Experiment #3 Conditions

T =

o C

 [KMnO 4 ] [H2C 2 O 4 ] time (s) Rate 3 = [KMnO 4 ]/time Trial 1 Trial 2 Trial 3

Trial 4

Trial 5

Average Rate

Standard dev.

95% conf.,

Determination of Reaction Order:

The results from the various pairs of experiments will now be combined to find X and Y. The conditions for Experiments #1 and #2 differ by the oxalic acid concentration, [H 2 C 2 O 4 ]. We can therefore use eq. 4 to give the reaction order with respect oxalic acid:

ln rate /rate

1

2

Y= ln

[H C O ] /[H C O ]

2

2

4

1

2

2

4

2

eq. 4

Substitute your values of rate 1 and rate 2 to obtain Y; remember that ln” is natural log not log base 10. Now we can use results from Experiments #1 and #3 to get a similar expression for the reaction order with respect to potassium permanganate.

ln rate /rate X= ln [KMnO ] /[KMnO ]

1

3

4

1

4

3

eq. 5

Substitute your values of rate 1 and rate 3 to obtain X.

Now we can write the overall rate equation, substituting numbers for X and Y:

rate = k [KMnO 4 ] X [H 2 C 2 O 4 ] Y

Then we can solve for the rate constant, k, using data from any of the three experiments.

k = [KMnO ] rate

4

X

2

4

]

Y

[H C O

2

eq. 6

The units of k depend on the values of X and Y. the rate has units of mol/L.s. Therefore, the rate constant has units of mol (1-X-Y) /L (1-X-Y) .s. As an example, if X = 1.5 and Y=0.5, the units of k are mol (1-1.5-0.5) /L (1-1.5-0.5) .s = mol -1 /L -1 .s = L/mol.s.

 Results: Reaction Order X (rounded to nearest 10 th ) Reaction Order Y (rounded to nearest 10 th ) Overall Order of Reaction X+Y Rate constant, k (with proper units) Questions:

Question #1: In this experiment you estimated the reaction rate by

rate = [KMnO 4 ]/time

Derive this expression from the more general relation given in eq. 1 by accounting for the fact that all the permanganate is converted to intermediate at time t? Based on your experimental observations, suggest another way to estimate the rate.

Question #2: Using your values of X, Y, and k, what would the rate be if [KMnO 4 ] = 0.0500 M and [H 2 C 2 O 4 ] =0.123 M?

Question #3: Each reaction condition was repeated in triplicate to enable the determination of the precision of the reaction rates. Recall, precision is represented by the width of the 95% confidence interval, 2. You will now use the s to estimate the precision of the reaction orders X and Y. Use the determination of X as an example. From eqn 5

ln rate /rate X= ln [KMnO ] /[KMnO ]

1

3

4

1

4

3

The numerator contains the ratio of two rates. This ratio is too large if rate 1 is too large and rate 3 is too small. Alternatively, if rate 1 is too small and rate 3 is too large, X will be too small. To incorporate the confidence limits we will use (rate+/2) and (rate-/2) to give estimates of the precision of X and Y. Here (rate+/2) represents the point half way to the upper confidence limit and (rate-/2) is half way to the lower confidence limit. The upper and lower bound of X (X + and X - ) become

X

+

=

ln (rate

1

1

/2)/(rate

3

3

/ 2)

ln [KMnO ] /[KMnO ]

4

1

4

3

X

=

-

ln (rate

1

1

/2)/(rate

3

3

/ 2)

ln [KMnO ] /[KMnO ]

4

1

4

3

Determine X + , X - , Y + and Y - from your data.

Question #4: The precision of the rate constant determination can be established in a similar manner to that employed in Q3 for the precision of X and Y. Defining

X +1/2 = (X + + X)/2

Y +1/2 = (Y + + Y)/2

X -1/2 = (X- + X)/2

Y -1/2 = (Y- + Y)/2

We can estimate the upper and lower bounds of k to be;

k

+

k

=

=

rate

 X  -1/2 KMnO 4   H C O 2 2 rate 4  Y -1/2 X  +1/2 KMnO 4   H C O 2 2 4  Y +1/2

Determine the upper and lower limits of the rate constant k from your data.

Experiment #6: Kinetics II - The Arrhenius Equation Reaction between Oxalic Acid and Potassium Permanganate

Objective: Determine the activation energy for the reaction of oxalic acid with potassium permanganate using a colorimetric analysis.

Background: In the previous experiment you determined the parameters of the rate equation for the reaction between potassium permanganate and oxalic acid.

KMnO 4 (aq) + H 2 C 2 O 4 (aq) purple colorless

=> products yellowish to colorless

The rate law expression gives the dependence of the reaction rate on the concentration of reactants. For the reaction under investigation, we wrote

rate = k[KMnO 4 ] X [H 2 C 2 O 4 ] Y

eq. 1

where the [ ] indicate molarity (moles/L) and X and Y are called the orders with respect to potassium permanganate (X) and oxalic acid (Y), respectively. The values of X and Y are not always integers; they are often fractions or decimal numbers. The overall rate order would be "X + Y". Finally the constant, k, is called the rate constant for the reaction and it is a constant at any one temperature. You have already observed that an increase in concentration of either reactant resulted in an increase in the rate of the reaction, reduction of the time required for the complete conversion of KMnO 4 . Provided the reactions were all conducted at the same temperature, the rate constant, k, likely was determined to be independent of reactant concentration. However, had the temperature been changed you would have discovered a dramatic change in the rate of the reaction and the rate constant. For many reactions it has been observed that the rate constant doubles for each temperature increase of 10 o C. In this experiment you will determine the temperature dependence of the rate constant for permanganate/oxalic acid reaction. When two molecules react, they must collide with each other with sufficient energy and with the correct orientation. Think of carrying some packages while walking in a crowd. If someone brushes against you, it might be annoying, but otherwise nothing happens. If, however, someone is running and bumps into you (high kinetic energy), they might knock off a package or two, or even knock you over completely. Conceptually it’s the same with colliding molecules. Low energy collisions don’t loosen the bonds of the molecules. Generally, there is a threshold energy that the collision must overcome to break and subsequently rearrange bonds (knock off the package). This threshold energy is called the activation energy. Recall that molecules in a fluid are in constant motion. At any given temperature some are moving slow and others are fast, have sufficient energy to overcome the activation

energy barrier. As the temperature increase, the fraction of fast moving molecules increases, thus increasing the chance of reactive collisions. The reaction rate is proportional to the fraction of collisions with energy in excess of the activation energy. This is mathematically described by the Arrhenius equation.

k

= Ae

E /RT

a

eqn. 2

Where k is the rate constant, A is referred to as a frequency factor, Ea is the activation energy

for the reaction in J, R is the gas constant (8.314 J/mol.K) and T is the absolute temperature in degrees Kelvin. In the previous experiment you measured the rate constant of the KMnO 4 /H 2 C 2 O 4 reaction at room temperature for various concentrations of the reactants. Now you will determine the rate for a single concentration, but at multiple temperatures. To determine the activation energy from the rate vs. temperature data it is most convenient to take the natural log of both sides of eqn. 2.

ln(k) = ln(A) + ln e

E

ln(k) = ln(A) - RT

a

E /RT

a

eqn. 3

Inspection of eqn. 3 reveals that a plot of ln(k) vs. 1/T should reveal a straight line, with a slope of E a /R and an intercept of ln(A).

Example: An experiment is run at 20.0, 30.0 and 40.0 o C using 6.00 mL of distilled water, 5.00 mL of 0.755 M H 2 C 2 O 4 (aq) and 1.00 mL of 0.130 M KMnO 4 (aq) for each run. The reaction rate at the three temperatures is given in Table 1. The table also gives values for 1000/T and ln(rate) to be used to construct a linear graph.

 Temp. o C rate (mol/L.s) 1000/T (1/K) ln(rate) 20.0 5.4x10 -5 3.41 -9.83 30.0 1.1x10 -4 3.30 -9.12 40.0 2.5x10 -4 3.19 -8.29