In the Laboratory

A Simplified Method for Measuring the Entropy Change of Urea Dissolution An Experiment for the Introductory Chemistry Lab
Charles A. Liberko* and Stephanie Terry Department of Chemistry, Cornell College, Mount Vernon, IA 52314-1098; *cliberko@cornellcollege.edu

As part of an effort to teach our introductory chemistry courses with a closer connection between the lecture and laboratory, we began modifying our laboratory exercises so that they were as relevant as possible to the topic being covered in lecture. Utilizing a workshop-type format, we often included mini-labs, which are short lab activities carried out by the students immediately after a topic is introduced in lecture. After completing the mini-lab, the students return to the lecture room for further clarification of key points. For the topics that are the most difficult to understand, we sought to avoid the introduction of complex techniques so that the main idea would not be lost in the details. By modifying an existing procedure, we have developed a laboratory exercise for measuring the thermodynamic values of the dissolution of urea, suitable for the introductory college or advanced high school level. While the concept of entropy is often covered at the introductory level, we experienced great difficulty in finding simple laboratory exercises to reinforce this concept (13). Complicated systems or indirect experimental measurements made these procedures unsuitable for our purposes. Pickering (1) has shown that the dissolution of urea is a particularly useful system for a laboratory determination of entropy. Urea dissolves rapidly in water, making it well suited for measuring the enthalpy change of dissolution. The process is spontaneous and endothermic, and is therefore driven by entropy. The equilibrium expression for the process can be simplified to that shown below so that in a saturated solution, the equilibrium constant can be approximated by the concentration of urea.1 In Pickerings procedure, a blood urea nitrogen (BUN) test was used to determine the concentration of urea in a saturated solution. The test requires extensive dilution of the sample and the construction of a Beers law plot in order for the spectroscopic determination to be made for urea. The instability of the analyte requires the measurements to be made rapidly after preparation. urea(s) + H2O() urea(aq) Keq = [urea] The Experiment: Implementation and Discussion To simplify this process and make it more suitable for use in a guided-inquiry format, we modified Pickerings procedure, determining the concentration of urea in a saturated solution by a more direct method. We found that if a known amount of urea (ca. 4 g) was placed in a 10-mL graduated cylinder and water was added slowly until the urea just dissolved, the concentration of the saturated solution could be directly

determined by dividing the number of moles of urea used by the final volume of the solution. While this rather crude approach may be unsuitable for an analytical lab, it has several advantages in an introductory lab. First, it is pedagogically simple. Given minimal guidance, students figure out how to do it and why they are doing it. The method is quick and the procedure (along with the measurement of H ) can be done multiple times in a typical lab period. The method does not rely on procedures such as Beers law analysis, electrochemistry, or titration, with which the students may not be familiar. It does not require any special equipment. It is not particularly sensitive to impurities or prone to errors so it is relatively student proof . The results obtained by this method are reasonable and compare favorably with results obtained using more complicated methods; moreover, the method is not only simple but also precise, making the results quite reproducible, as is shown by the reported errors (Table 1). However, comparison of the values obtained by this method with the accepted values shows that this method gives values of G that, although reasonable, are consistently too positive.2 Our students are given a prelab exercise in which they write the equilibrium expression for the dissolution of urea. They then must think about how they could actually measure Keq. They work in groups and discuss their ideas with each other while the instructor circulates and offers advice. Finally, the students are asked to outline a procedure for the determination of H , G , and S for the process. This forces them to think about what quantities can actually be measured and which are calculated from measured quantities. After turning in the prelab exercise, the students are given a terse set of guidelines and suggestions for performing the lab. For the determination of H, they are given a polystyrene foam coffee cup calorimeter and a thermometer. It is suggested that dissolving enough urea to make a 1 M solution would be reasonable for determining the heat of dissolution. They are told to assume that the heat capacity of the urea solution is
Table 1. Thermodynamic Values for Urea Dissolution Variable H/kJ mol 1 G/kJ mol 1 S/J mol 1 K 1
aReported

Valuea Exptl 13.7 1.9 5.77 0.04 65.2 6.3 Pickering (1) 17.6 7.2 5.77 0.63 77.0 28 Acceptedb 14 6.86 69.5

errors are standard deviations. bAccepted values are from Keller, R. Basic Tables in Chemistry ; McGraw-Hill; New York, 1967 (as reported by Pickering [1]).

JChemEd.chem.wisc.edu Vol. 78 No. 8 August 2001 Journal of Chemical Education

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In the Laboratory

essentially that of pure water (4.184 J C 1 g 1). It is left for the students to discover that the process is endothermic. For the determination of the equilibrium constant, Keq, the students are told that about 1 g of urea will dissolve in 1 g of water. It is suggested that they place a known amount of urea in a graduated cylinder and slowly add water with good mixing until the urea just dissolves. They are reminded that they will need to know the final temperature of their saturated solution and that the accepted values were measured at 25 C. After the lab, the students meet again with their group and pool their data. It is necessary at that point to review the differences between H and H . While the students actually determined a H, it is reasonable to assume that in this case H is a good approximation for H because the urea solution was approximately 1 M. With the values of H and Keq, each student then calculates G and S . The pooled results are compared with accepted values and possible sources or error are discussed. The students are asked to justify from a molecular level why their values for H and S were positive or negative. Hazards Urea, CAS registry number 57-13-6, is an irritant. Conclusions This method for the determination of thermodynamic data of urea dissolution has the advantage of being quite simple, both conceptually and practically. It does not require special equipment or instrumentation. Introductory students can carry out the entire procedure in less than two hours and obtain quite reasonable values. The guided-inquiry format forces students to think about what they are doing and why they are doing it. The concept of entropy is reinforced by this laboratory experience, not further obscured by complicated laboratory procedures. Acknowledgments This work was supported by Cornell College. Cindy Strong was helpful in the preparation of the manuscript.

Supplemental Material

Student handouts and instructor notes are available in this issue of JCE Online. Notes
1. Concentration is substituted here for activity, which is not typically introduced at this level. 2. In simplifying heterogeneous equilibrium constant expressions, it is typical to make the assumption that for dilute solutions the concentration of the solvent does not vary from that of its standard state and is therefore ignored. Using this assumption, our measured Keq was 10.24 0.15 mol L1. Owing to the high concentration of urea in a saturated solution, this assumption is not valid. By measuring the total water added to the solution, we have determined the concentration of water in a saturated solution of urea at 25 C to be 31.0 M and not 55.5 M as in pure water. Thus the equilibrium constant becomes urea(s) + H2O() urea(aq)

K eq =

[urea] [urea] = water(soln) / water(pure) 31.0 M/55.5 M

Making this substitution, we can recalculate our Keq to be 18.36 0.98 mol L1. Our G then becomes 7.20 0.13 kJ mol 1, which is much closer to the accepted value of 6.86 kJ mol 1. Using these corrected values, the calculated S is then +70.3 6.7 J mol 1 K1, which compares favorably with the accepted value of +69.5 J mol 1 K1.

Literature Cited
1. Pickering, M. J. Chem. Educ. 1987, 64, 723 and references cited therein. 2. Monroe, M. B.; Abrams, K. J. A Course in Experimental Chemistry, Book II ; Freeman, Cooper & Company: San Francisco, 1984; pp 256260. 3. Scaife, C. W. J.; Beachly, O. T. Chemistry in the Laboratory; Saunders: Philadelphia, 1987; pp 281292.

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