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EXPERIMENT 7: Determination of Ksp, H, S, & G for the Dissolution of Borax

The laws of classical thermodynamics apply specifically to the equilibrium condition of a system. When these laws are applied to chemical reactions, they relate the equilibrium condition and the temperature of a given reaction to the thermodynamic quantities, H, S, and G, which specify respectively the change in enthalpy, entropy and free energy for the system. By experimentally studying the effect of temperature on the equilibrium condition for a chemical reaction, we can obtain the fundamental information that we need to calculate these important thermodynamic functions. This experiment investigates the effect of temperature on the solubility of the sparingly soluble salt, sodium tetraborate decahydrate, Na2B4O710H2O, also known as borax. Borax is an example of a class of compounds called borates, which contain polyanions composed of trigonal BO3 and/or tetrahedral BO4 units linked by bridging oxygen atoms to form chain or ring structures. These structural features of the tetraborate anion suggest that it would be more appropriate to represent borax by the formula Na2[B4O5(OH)4]8H2O. Borax occurs naturally in dry lake beds in California and the southwestern United States. These beds have long been important sources of this valuable mineral. Common uses of borax are in soap and other cleaning products, as a flux for solder, as a preservative, and in the manufacture of glass. Sodium tetraborate dissociates in water to form sodium and borate ions: Na2[B4O5(OH)4]8H2O(s) 2 Na+(aq) + B4O5(OH)42-(aq) (7.0) (7.1) The solubility product (equilibrium) constant, Ksp equation is: Ksp = [Na+]2 [B4O5(OH)42-] Note that two sodium ions are produced for each borate ion in the reaction. Therefore the concentration of Na+ is twice the concentration of borate ion. If we let s represent the concentration of tetraborate ions in solution at equilibrium, then Na+ ions must equal 2s. Substituting these values into the equilibrium expression the equation becomes: Ksp = (2s)2 (s) = 4s3 (7.2) Finding the concentration of borate ion, in any sample at any given temperature, leads directly to a value for the solubility product at that temperature. Determination of the borate ion concentration is based on the principle that it is a weak base. It reacts with water to form the hydroxide ion (OH-), a strong base, and boric acid (H3BO3), an extremely weak acid: B4O5(OH)42-(aq) + 5 H2O 4 H3BO3(aq) + 2 OH-(aq) (7.3)

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The concentration of the borate ion can be determined by a simple acid-base titration. In this experiment, the hydroxide ion in saturated Borax solutions is titrated with hydrochloric acid to a bromocresol green end point: B4O5(OH)42-(aq) + 2 HCl(aq) + 3 H2O 4 H3BO3(aq) + 2 Cl-(aq) (7.4) This titration data allows for calculation the equilibrium constant for the reaction. This general procedure is repeated for borate ion-containing samples of constant volume obtained at various temperatures. Calculation of these temperature dependent Ksp values is but the first step in a greater sequence of obtaining thermodynamic parameters for the dissolution of borax in water. Since Grxn = Hrxn T Srxn and Grxn = - RT ln K H S rxn rxn ln K= + RT R (7.6) it follows that in the standard state, the equilibrium constant is related to enthalpy and entropy change of reaction as: (7.7) (7.5)

Equation 7.7 allows us to calculate an equilibrium constant from fundamental thermodynamic data. Alternatively, we can estimate values for H and S from the equilibrium constant. Equation 7.7 has the form: a ln K= + b (7.8) T Where a and b represent -H/R and S/R respectively. We can assume that H and S are constant over some temperature range (this is likely to be the case provided the temperature interval is small), then a plot of ln K versus 1/T will have a slope of -H/R and an intercept of S/R. Thus the measurement of ln K made over a range of temperature and plotted vs. 1/T provide estimates of H and S values for the reaction. We can then of course calculate G directly from equation 7.5.

Additional Pre-Lab Reading

Lab Skills YouTube videos (see CLEW/Resources/LABS): Burets and Titration. Report Guidelines (see CLEW/Resources/Labs): (7) Discussion. Chemistry, A Molecular Approach, 2nd Ed., Tro, N., Section 17.9.

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Chemicals and Reagents

0.50 M HCl (standardized) Borax, Na2B4O710H2O (30 32 g) Bromocresol green indicator

Glassware and Equipment

Balance (0.01 g) Beakers (2): 250, & 400 mL Buret: 50 mL Erlenmeyer flask: 125 mL Graduated cylinders: 10, 25, 50 mL Hot plate Retort stand and buret clamp Short stem funnel Stirring rod Test tubes: 3 Test tube rack Vernier computer interface Vernier temperature probe

Procedure
1. 2. 3. 4. Connect a temperature probe to CH1 of the LabPro interface. From the LABS folder located on the computer desktop, launch the LoggerPro software. Set aside three test tubes, a 125 mL Erlenmeyer flask, a 10 mL graduated cylinder, and pre-heat approximately 150 mL DI H2O in a 250 mL beaker for future use Obtain approximately 3032 g of Borax directly into a second 250 mL beaker. Add 150 mL DI H2O and mix. Heat on the hot plate, stir occasionally, and monitor the temperature. The temperature should not exceed 50C. If all of the solid borax dissolves, add a little more until a small amount of excess solid is present and you are sure the solution is completely saturated. Remove the saturated solution from the heat once the temperature has reached 50C and allow it to cool while monitoring the temperature. Borax will crystallize as the solution cools so make sure you are measuring the temperature of the liquid and not the solids at the bottom of the beaker. When the solution cools to 45C, carefully pour 5.0 mL of the top liquid layer, trying not to disturb the bottom solids, into a 10 mL graduated cylinder. Quickly transfer this to a 125 mL Erlenmeyer flask. Record the actual solution temperature at the time of transfer. Rinse the graduated cylinder with the pre-heated warm DI H2O water from the warm water bath and add the washings to the flask. When the solution cools to 40C, again, pour 5.0 mL into the 10 mL graduated cylinder. Quickly transfer this to a test tube. Record the actual solution temperature at the time of transfer. Rinse the graduated cylinder with water from the warm water bath and add the

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washings to the test tube. Repeat this same procedure to obtain samples as 35C and 25C. 8. 9. 10. 11. 12. Fill and prepare a buret with standardized HCl titrant. Add 50 mL DI H2O to the sample in the Erlenmeyer flask along with a few drops of bromocresol green indicator. Titrate to a yellow endpoint. A white sheet of paper under the beaker may help identify the end point. Discard the contents of the contents of the flask to the waste container and wash it out. Pour the sample from the first test tube into the clean flask (does not need to be dry) and rinse the tube with DI H2O, adding the washings to the flask. Add DI H2O to a volume of approximately 50 mL followed by a few drops of indicator. Titrate to a yellow end point with HCl. Repeat for the remaining samples. Calculate Ksp before proceeding. (See Data & Results question 1, Table 7.1). Plot a graph of Temperature (C) vs Ksp as follows: a. Disconnect your temperature probe from the interface. b. Choose New from the File menu. An empty graph and table will be created in Logger Pro. c. Double-click on the x-axis heading in the table, enter a name and unit and then enter the four values for Temperature (C) from your data table. d. Double-click on the y-axis heading in the table, enter a name and unit and then enter the four solubility product constant values. 15. Plot a graph of ln Ksp vs. 1/T as follows: a. Choose New Calculated Column from the Data menu. b. Create a column, ln K. c. Create a second column, 1/(temp (C) + 273). d. On the displayed graph, plot ln K on the y-axis and 1/T on the x-axis by clicking on the respective axes labels. Autoscale the graph if necessary. e. Click the Linear Regression button, Data & Results question 2). . Record the equation of the line. (See

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Name: Lab Partner:

Date: Section:

Report 7: Determination of Ksp, H, S, & G for the Dissolution of Borax

Data and Results
1. Calculate the concentration of borate ion for each titration. Use the borate ion concentration to determine Ksp and ln Ksp at each temperature. Show all calculations on a separate sheet (or back of page if blank). Summarize results in Table 7.1 [6.0]

Concentration of Standard HCl (from bottle): ____________________ Table 7.1 Temp., C Temp., K 1/T (K-1) Final buret reading Initial buret reading Vol. HCl Moles H+ Moles B4O5(OH)42Molarity B4O5(OH)42Ksp ln Ksp Solution 1 Solution 2 Solution 3 Solution 4

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Name:

Section:

Data and Results (cont.)

2. Calculate H, S, and G. Show all of your work and include all units. [6.0]

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Name:

Section:

Discussion [3.0]
Briefly discuss the following according to your experimental results: i. ii. iii. What does the magnitude of Ksp values obtained for the various temperatures tell you about the effect of temperature on the solubility of borax? What does the calculated value of G298 tell you about this reaction? Does the reaction favour products or reactants? Why? Does your value for H suggest that the solvation of borax is endothermic or exothermic? Explain.