NAME: Arthur Keenan ID Number: 0930861

Quiz Section: AC Lab Partner: RJ Keeley

Note: All sections of this report must be typed

Chem 152 Experiment #4: Thermodynamics II

The Temperature Dependence of the Solubility Product, Heat of Solution, and Entropy of Solution of Potassium Hydrogen Phthalate
Total Points = 60 (5 notebook, 55 template)

By signing below, you certify that you have not falsified data, that you have not plagiarized any part of this lab report, an d that all calculations and responses other than the reporting of raw data are your own independent work. Failure to sign this declaration will cost you 5 points.

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PURPOSE AND METHOD

How are the solubility products (Ksp) of KHP at various temperatures determined? (3 pts) [K+] = [HP-] so Ksp = [K+][HP-] = [HP-]^2 Titration means the moles of HP will the same as the moles of NaOH titrated in the solution. This will allow us to calculate the [HP] of 1 mL of the solution, based on the NaOH added.

How is Ksp in a saturated solution of KHP in 0.50 M KCl determined? (3 pts) We determine [K+] in the KHP + .5 KCl solution by measuring the emission intensity of the K+ standards with the photometer. Using our curve established by various measurements with the photometer, we can then calculate the [K+]. [HP-] is still going to be measured by titrating NaOH in the solution, and allowing us to calculate the [HP-] Ksp is still equal to [K+] and [HP-] so by knowing the [K+] from the photometer, we can multiply that with the [HP-] found from the titration and figure ourt Ksp.

DATA AND CALCULATIONS A. Flame emission determination of [K+] in the 0.50 M KCl + KHP (sat) solution
Preparation of Standards Table 1: Volume of 5.00x10-3 M needed to make 50 mL of each standard solution (from prelab) Standard [K+], (M) 1 7.50 E-5 2 1.50 E-4 3 2.25 E-4 4 3.00 E-4 5 3.75 E-4 mL of stock 0.75 1.50 2.25 3.00 3.75 DATA Table 2: Flame Photometer Data Solution Standard 1 Standard 2 Standard 3 Standard 4 Standard 5 [K+], (M) 7.50E-05 1.50E-04 2.25E-04 3.00E-04 3.75E-04 Temperature,oC KHP(sat) in 0.50 M KCl
Plot of Intensity vs [K+] (M) 400 Intensity vs a [K+](M) Add a Trendline and Trendline Eqn and on your plot and be sure to include titles for the plot and each axis.
350 400 300 350

Intensity 75 150 230 295 375 Intensity 308

27

250 300
Intensity Intensity

250 200
200 150 150 100 100 50 50 00 7.50E-05 0.00E+00 1.50E-04 1.00E-04 2.25E-04 2.00E-04
[K+](M) [K+] (M)

3 pts
Intensity Intensity

y = 993333x + 1.5

5.00E-05

1.50E-04

2.50E-04

3.00E-04 3.00E-04

3.50E-04

3.75E-04 4.00E-04

slope y-intercept

9.93E+05 M-1 1.5

Table 3: Flame Emission Determination of [K ] in the original sample Temperature, oC 27 [K ] in Measured Solution (M) 3.171E-04
+

Dilution factor 2,500

[K ] in Original Solution (M) 0.829

Type the calculation you used to determine [K+] in the measured and original solutions above. x = [K] in measured solution. 331 = 993333(x) + 1.5 x =3.32 * 10^-4 x * 2500 = .8293
3 pts

B. Standardization of NaOH
Table 4: NaOH Standardization Run 1 Mass of KHP, g moles KHP Initial buret reading, mL Final buret reading, mL mL NaOH titrated L NaOH titrated [NaOH], moles/L Average, [NaOH] 0.132 0.00065 0 6.8 6.8 0.0068 0.095 Run 2 0.132 0.00065 0 6.60 6.60 0.0066 0.098 0.097 M Run 3**

Type the calculation for determining [NaOH] for one of the runs. (6.65 x 10^-4) moles / .0068 L = .095 **If you only performed two titrations, type the calculation that you used to determine that you did not need to do a third titration.
3 pts

C. Titrations of KHP Samples with and without KCl

mL of KHP(aq) used in titrations 1.00 mL Guide for completing Table 5: Move from left to right in this table, entering your data and doing the calculations necessary for the next column. Calculations: a) convert T to Kelvin, 2) calculate mL of NaOH added, 3) calculate the mmoles (10-3 moles) of NaOH added (1:1 reaction, so moles NaOH added equal moles of HP- present), 4) molarity of HP- (from mL and moles), 5) Ksp from [HP-], and then 1/T and ln Ksp for the plot below. Let Excel help with the calculations: enter your data for temperature and buret readings, then type the necessary formulas in the first cell of each of the other columns and copy the formula to the cells below it down the column.

Table 5: Titration Data and Calculations

Temperature, oC 3.0 22.7 34.7 39.9 58.7 60.2 Temperature, K 276.2 295.9 307.9 313.1 331.9 333.4 Initial buret reading (mL) 0.00 0.00 0.00 0.00 0.00 0.00

DO NOT enter the data for the solution with KCl in this table
Final buret reading (mL) 2.75 1.90 5.45 6.85 10.35 12.00 mL NaOH added 2.75 1.90 5.45 6.85 10.35 12.00 mmoles HP(=mmoles NaOH) 0.265 0.179 0.526 0.661 0.999 1.158 Molarity HP0.265 0.179 0.526 0.661 0.999 1.158 Ksp 0.0704 0.0319 0.2766 0.4370 0.9976 1.3410 1/T (in K) 0.00362 0.00338 0.00325 0.00319 0.00301 0.00300 ln(Ksp) -2.653 -3.446 -1.285 -0.828 -0.002 0.293

Type the calculations you performed for the Room Temp (~22 C) solution. (2pts each) mmoles NaOH: .0965 M * 2.7 mL = .265 mmol [HP-]: .259 mmol / 1 mL = .259 M

Ksp: [K+] * [HP-] = .259 * .259

Plot of0.500 ln(Ksp) vs 1/T(K) Add a Trendline and Trendline Eqn and on your plot and be sure to include ln(Ksp) a titles vs for 1/T(K) the plot and each axis.
0.000 0.500 0.00000 -0.500 0.000 0.00362 -1.000 -0.500 ln(Ksp) -1.500 -1.000 -1.500 -2.000 0.00050 0.00100 0.00150 0.00200 0.00250 0.00300 0.00350 0.00400

3 pts

0.00338

0.00325

0.00319

0.00301

0.00300

ln(Ksp)
ln(Ksp)

-2.000 -2.500
-2.500 -3.000 -3.000 -3.500 -3.500 -4.000 -4.000 1/T (K)

y = -5485x + 16.467

slope y-intercept

-4555 K 13.762

R DHoSoln DSoSoln

8.314 J/mol*K 37868.6 114.4

Typeyour calculations for DH and DS.

(2 pts each)

DH = -slope * R = 4554.8 * R = 16203.986 DS = 13.762 * R = 144.4

Table 6: Titration of RT (no KCl) solution with NaOH(aq) to determine [HP-] Temperature, oC 22.7 22.9 22.9 Initial buret reading (mL) 0.00 0.00 0.00 Final buret reading (mL) 1.90 1.85 1.85 mmoles* NaOH mL NaOH titrated (=mmoles HP) 1.90 0.18 1.85 0.179 1.85 0.179 Average M 1.00 mL 0.032 Molarity HP0.18 0.179 0.179 0.179
autofills from Table 5

mL of KHP(aq) used in titrations Ksp at room temperature (no KCl) (from Table 5 and two more replicates) Table 7: Titration of RT KHP in KCl with NaOH(aq) to determine [HP ] Temperature, oC 24 24 24 Initial buret reading (mL) 0.00 0.00 0.00 Final buret reading (mL) 9.30 9.25 9.25
-

2 pts

mmoles* NaOH mL NaOH titrated (=mmoles HP) 9.30 0.763 9.25 0.893 9.25 0.893 Average M:

Molarity HP1.763 0.086 0.086 0.645

2 pts

mL of KHP(aq) in KCl used in titrations Ksp in 0.50 M KCl (from Tables 3 and 7)

1.00 mL 0.604

Type the calculations for Ksp in 0.50 M KCl above and the % difference between the two K sp values you obtained. Ksp: [K+][HP-] = .797 * .758 = .604

4 pts

% difference : KHP vs KHP/KCl, both at room temp ((.604-.205) / .604) * 100 = 66.06%

RESULTS AND DISCUSSION

1. Using a 15% difference as acceptable, are the room temperature K sp values with and without KCl the same? 2 pts
No. Not really. We calculated a 66.06% difference between with the KCl and without. It's somewhat concerning. Consulting a peer, I learned that he got a largely different measurement of mL titrated when it came to the KCl portion. I'm not sure why we needed so much for our titration.

But yes, I suppose it is possible the KCl actually changes the Ksp, if we were just looking at OUR results.

2. Based on your results at room temperature, what is the solubility of KHP in g/L
Ksp = [K+][HP-] = .205 x = [K] x^2 = Ksp x = .453 Molar solubility .453 * molar mass = .453 * 204.221 =92.51

3 pts

3. What will happen to the solubility and Ksp when NaOH(aq) is added to a satuared solution of KHP. Explain your reasoning.
KHP + NaOH = H2O + P2
Equilibrium will go to the right, and so, solubility will increase.

4 pts

4. What will happen to the solubility and Ksp when HCl(aq) is added to a saturated solution of KHP. Explain your reasoning.
By adding the HCL, the solution becomes oversaturated with undissociated KHP, that precipitates. So, the Ksp is reduced. HCl also increases concentration of H+ ions, causing the equilibrium to shift to the left, and solubility will decrease.

4 pts

5. Based on a previous quarter, DHoSoln = 34.1 kJ/ mole and the DSoSoln = 120 J/Kmole. How do your results compare (calculate and comment on % difference)?
For some reason, they got an H value TWICE ours, and a S THREE times ours. I have no idea how this happened. This is largely dependent on the slope. My slope, for whatever reason, is not steep enough.

3 pts

6. What is the biggest source of error in the determination of the K sp values?

There probably was a mistake in the titration process, giving us an unusually large amount, especially during the titration with th e KCl added. It's also possible I made a mistake somewhere in my calculations but going back and reviewing does not reveal to me what mistake I made .

2 pts

Laboratory Waste Evaluation (1 pt)

Laboratory waste is considered anything generated during an experiment that is disposed of down the sewer drain, thrown in the garbage, collected in a container for disposal by the UW Environmental Health & Safety department, or released into the environment. Based on the written lab procedure and your actions during the lab, list the identity and approximate amount (mass or volume) of waste that you generated while performing this experiment.
A lot of NaOH is titrated, approximately 92 mL of it. This was titrated in 11 mL of KHP solution, as well as about .45 grams of solid KHP. These were dissolved in solutions with deionized water. To create the calibration curve with the photometer, a lot of standard solutions were created, using about 250 mL of the solution, which consisted of 75 mL of K solution, the rest being deionized water. An unknown amount of paper towels were harmed in the making of this experiment.