EXPERIMENT NO.

Calorimetry

Avila, Romar Angelo M.

Department of Mining, Metallurgical and Materials Engineering, College of Engineering, University of the Philippines, Diliman, Quezon City, Philippines

Introduction In chemistry, scientists often encounter the problem of having to measure heat changes of systems. A calorimeter is used in these instances. By knowing either the mass and specific heat or the heat capacity of the calorimeter, plus the change in temperature, one can solve for the heat of reaction, qrxn [1]. There are two types of calorimeter: the constant-pressure or bomb calorimeter used for combustion reactions and the constant-volume or coffee cup calorimeter used to for noncombustion reactions such as neutralization and oxidation-reduction (redox) reactions [2]. In the experiment, a constant-volume calorimeter is used to measure heat changes in four types of reactions: neutralization, acid-active metal reaction, metal displacement, and precipitation reaction. The reactions involving acids and bases will also vary in terms of the relative strengths of the compounds in solution. [1] Petrucci, R.H.; Herring, F.G.; Madura, J.D.; Bissonnette, C. General Chemistry:

Principles and Modern Applications, 10th ed; Pearson Education Inc: Philippines, 2012; pp 248251 [2] Chang, R. Chemistry, 10th ed; McGraw-Hill Publishing: New York, NY, USA, 2010; pp

247-249

Answers to Questions Posted on the Bulletin Board Calibration of the Calorimeter 1. Give the net ionic equation of the reaction used to calibrate the calorimeter. H(aq) + OH(aq) H2O(l)

a. Is the reaction endothermic or exothermic? The reaction is exothermic, since heat was released to the surroundings by the system during the reaction. b. Which is the limiting reactant? (10mL NaOH)(1L/1000mL)(1mol/1L) = 0.010mol NaOH (5mL HCl) (1L/1000mL)(1mol/1L) = 0.005mol HCl HCl is the limiting reactant, since there are only 0.005mol of it compared to 0.01mol of NaOH. c. How much (in moles) limiting reactant was used? As seen from the calculations above, the number of moles of HCl used in calibration is 0.005mol. d. How much heat was generated (or absorbed) by the reaction? (-55.8kJ/mol)(0.005mol)(1000J/1kJ) = 297J 279J were released by the system to its surroundings. 2. Relate the sign of the T to the H of the reaction used for calibration. The sign of T determines the sign of the qcal, which is the opposite sign of qrxn: qcal = mcT; qcal = -qrxn So, -qrxn = mcT. In turn, -qrxn = -nH. We can form another relation, which is: -nH = mcT

Since n (number of moles) is always positive, the negative sign is multiplied to H. Therefore, we can conclude that the sign of T will be directly proportional but opposite the sign of H. 3. What is the heat capacity of the calorimeter? Relate its sign to the sign of the T. The heat capacity of the calorimeter (Ccal) is the amount of heat energy needed to raise the temperature of the calorimeter by 1C. This takes into account both the specific heat and the mass of the calorimeter. In the experiment, the author of this paper got a value of 79.7J/ C. The Ccal and T are used to calculate the qcal: qcal = CcalT There is no straightforward relationship between the signs of C cal and T. However, we do know that Ccal is always a positive value, since its factors (mass and specific heat) are always positive. 4. In the appendix, show the derivation to obtain the equation used to calculate the heat capacity of the calorimeter. Determination of Heats of Reaction 5. Give the net ionic equation for each reaction. a. NH3(aq) + H(aq) NH4(aq) H2O(l) + CH3COO(aq) NH4(aq) + CH3COO(aq)

b. CH3COOH(aq) + OH(aq) c. NH3(aq) + CH3COOH(aq) d. H(aq) + OH(aq) e. Mg(s) + 2H(aq) H2O(l)

Mg(aq) + H2(g) Mg(aq) + CH3COO(aq)

f. Mg(s) + CH3COOH(aq) g. Zn(s) + Cu(aq) h. CO3(aq) + Ca(aq)

Zn(aq) + Cu(s) CaCO3(s)

6. Determine the limiting reactant and the amount of the limiting reactant in each of the reactions performed.

7. Calculate for the theoretical and experimental enthalpy of each reaction.

8. Relate the sign of T to the sign of the experimental H. Like in the explanation above in item number 2, the sign of T will be directly proportional but opposite the sign of H. 9. For reactions 1-4, which pair gave the most and the least exothermic (or endothermic) reaction? Explain the observation. (Use both the theoretical and experimental values for this) The theoretical values of the neutralization reactions are close to one another, as shown below. Table 1. Theoretical and Actual Enthalpies for Neutralization in Experiment 1 Reaction NH3 + HCl NaOH + CH3COOH Theoretical Hrxn -52.2kJ/mol -56.1kJ/mol Actual Hrxn -55.8kJ/mol -55.8kJ/mol % Error 6.93% 0.445%

NH3 + CH3COOH NaOH + HNO3

-52.5kJ/mol -55.8kJ/mol

-55.8kJ/mol -55.8kJ/mol

6.35% 0.00%

The students were limited to two significant figures due to the calibration of the thermometers, so the values are rounded off. This could explain why they recorded the same H rxn for all

four reactions. The fourth reaction has a 0.00% error because its net ionic equation is the same as the reaction used for calibration, which is:
H(aq) + OH(aq) H2O(l)

10. For reactions 5 and 6, which gave the most exothermic reaction? Why? (Use both the theoretical and experimental values for this) The active metal and acid reactions produce hydrogen gas as a product. This caused the test tube to pop periodically while performing the experiment. Since the popping transferred heat and matter to the surroundings, the solution can no longer be called adiabatic and isobaric as the system did work through expansion. This led to a large deviation in the theoretical and actual enthalpy values in the experiment. Table 2. Theoretical and Actual Enthalpies for Active Metal and Acid Reactions in Experiment 1 Reaction Mg + HCl Mg + CH3COOH Theoretical Hrxn -466.85kJ/mol -467.35kJ/mol Actual Hrxn -387kJ/mol -271kJ/mol % Error 17.1% 42.0%

11. For reactions 7 and 8, what are the solid products of the reaction? What is the theoretical yield of each? To get the theoretical yield, we must multiply the moles of limiting reagent (after applying their stoichiometric ratios) with the molecular weight of the precipitate. Table 3. Table of Molecular Weights for Precipitation Reactions in Experiment 1 Precipitate Cu(s) CaCO3(s) Moles LR 0.00764mol (Zn) 0.005mol (none) Molecular Weight 63.5g/mol 100.1g/mol

After multiplying we get 0.485g Cu and 0.501g CaCO3.

12. The net ionic of reaction 8 is a synthesis (combination) reaction. Using the theoretical H of the reaction, deduce the relative magnitude of the energy of bond breaking and bond forming during the reaction. The reaction between CaCl2 and Na2CO3 is endothermic. This means that it absorbed energy from its surroundings during the course of the reaction. The reaction can be broken down into 3 basic steps: CaCl2(aq) Na2CO3(aq) Ca(aq) + CO3(aq) Ca(aq) + 2Cl(aq) 2Na(aq) + CO3(aq) CaCO3(aq) H1 = positive H2 = positive H3 = negative

H1 and H2 are processes that involve bond breaking, thus they require energy from the surroundings. On the other hand, H3 is a bond forming process, which releases energy in order to gain stability. Observing the theoretical Hrxn for reaction 8, we see that it is a positive value, and this shows that the energy gained from dissolution (H 1 and H2) is greater than the energy gained from precipitate formation (H 3). |H1 +H2| > |H3| 13. In the appendix, show the equation used to determine the heats of reaction for reactions 1-6 and reactions 7 and 8. 14. Tabulate the possible sources of errors and their effect to the following parameters: T, Ccal, and H. Accompany each with a reason. Source of Error Mg ribbon not cleaned well Entire test tube not covered by Styrofoam Excess HCl used in calibration Excess NaOH used in calibration One pipette was used for transferring all compounds Effect on T Decrease Decrease Increase Decrease Decrease Effect on Ccal Not Affected Increase Decrease Increase Increase Effect on H Decrease Decrease Increase Decrease Decrease

Excess reactant mistaken for limiting reactant during calibration Stopper pops due to gas buildup Mg ribbon not cleaned well

Not Affected

Increase

Decrease

Decrease

Not Affected

Decrease

The MgO surface of the ribbon does not allow complete dissociation in acid. Small amounts of the impurities will remain, absorbing some of the heat released during the process. Thus, the T will be lower than the actual value. Ccal will be unaffected since its value was calculated in the calibration part of the experiment, while the H will decrease as it is directly proportional to T at constant Ccal. Entire test tube not covered by Styrofoam Styrofoam insulates the calorimeter, preventing the escape of heat. Exposing even a small part of the calorimeter will allow heat to flow out of that area, giving a lower T. C cal increases because it is inversely proportional to T, while H decreases because it is directly proportional to T. Excess HCl used in calibration HCl is the limiting reactant, so an increase in the volume used will increase the T, since more moles of HCl and NaOH will be reacting. Since Ccal is inversely proportional to T, the Ccal will decrease. H is constant in the calibration part (-55.8kJ/mol), but in the other reactions it will be higher since it is directly proportional to T. Excess NaOH used in calibration Since NaOH is the excess reactant, an increase in the volume used will not increase the number of moles that will react. It will instead lower T because the extra volume absorbs some of the heat of the reaction compared to the reaction with 10ml 1M NaOH. The C cal increases because it is inversely proportional to T, while the H will decrease, except in calibration where it is constant.

One pipette was used for transferring all compounds Using only one pipette for different compounds will affect the actual number of moles of the compounds used. The pipette may, for example, be used to transfer NaOH first then HCl. We may not see it, but small amounts of NaOH will be left in the pipette, and when it is used to transfer HCl, the excess NaOH will react thereby reducing the moles of limiting reagent. Thus, we are left with a lower T and H because of the decrease in moles, and a higher C cal. Excess reactant mistaken for limiting reactant during calibration Human error is a crucial factor that affects how the overall result of the experiment appears. If NaOH is mistaken to be the limiting reactant instead of HCl, the moles to be used in calibration will be 10mmol, which is twice the correct value of 5mmol. T will not be affected since its value depends on the actual moles of limiting reagent and is calculated experimentally. C cal and H, however, are calculated theoretically, and substituting the moles of excess reagent for the moles of limiting reagent we get a higher Ccal and a lower H. Stopper pops due to gas buildup The calorimeter is supposed to be at a constant volume at all times. In the reactions involving magnesium, one of the products is hydrogen gas, which causes pressure to build inside the test tube. When the stopper pops, the system does work on its surroundings, causing a loss of energy. Thus, some of the energy that can be used to increase the temperature is lost, causing a decrease in T. Ccal is unaffected since its value was calculated in the calibration part, while the H will decrease since it is directly proportional to the temperature change.

Answers to Questions in the Laboratory Manual 1. After obtaining experimental values of Hrxn, explain any discrepancy of the values to the theoretical. Give some possible sources of errors. There are many possible causes to the discrepancies in the value of H rxn. First, the system is imperfectly adiabatic; some heat is absorbed by the Styrofoam and some heat is supposed to

leave the system through the thermometer, which gives the reading. The instruments themselves such as the thermometer and balance are calibrated to only a specific decimal place, which means that small differences will not be detected. Rounding off is also a possible cause, since we follow significant figures in solving for H rxn. Lastly, there are the problems with the preparations and equipment stated earlier in number 14 of the answers to questions posted on the bulletin board. Here is the list again, which gives seven examples. Source of Error Mg ribbon not cleaned well Entire test tube not covered by Styrofoam Excess HCl used in calibration Excess NaOH used in calibration One pipette was used for transferring all compounds Excess reactant mistaken for limiting reactant during calibration Stopper pops due to gas buildup Effect on T Decrease Decrease Increase Decrease Decrease Not Affected Effect on Ccal Not Affected Increase Decrease Increase Increase Increase Effect on H Decrease Decrease Increase Decrease Decrease Decrease

Decrease

Not Affected

Decrease

2. In the procedure for the determination of H, explain why it is important: a. that the total volume of the resulting solution be 15ml? The calorimeter used is a constant-volume calorimeter. The volume used to calibrate the calorimeter must be the same in all reactions to give the same initial volume and pressure, which affect the energy changes in the reaction. b. to know the exact concentrations of the reactants? The concentration of reactants are vital in thermochemical calculations. If the experimental values deviate from the real values, there will be many errors, especially in equations involving the limiting reagent, especially qrxn and Hrxn.

c. to know the exact weight of the metal solids used? The solids present at the end of the reaction absorb some of the heat released by the reaction. We must take this into account so that the values of q rxn and Hrxn will become more accurate.

3. The neutralization of 200mL 0.5M HA by sufficient amount of NaOH evolves 6.0kJ of heat. a. Calculate the enthalpy change for the neutralization of 1 mole HA (200mL)(1L/1000mL)(0.5mol/1L) = 0.1mol Hrxn = qrxn/nlr = -6kJ/0.1mol = -60kJ/mol The Hrxn is quite close to the theoretical value, -56.1kJ/mol. b. Is HA a weak or strong acid? Justify your answer using thermochemical equations. Acetic acid is known to be a weak acid because it does not completely ionize in solution. Strong acids have this net ionic equation when reacted with strong bases: H(aq) + OH(aq) H2O(l)

The first ionization of all strong acids follow this; the anions do not participate in the reaction and are merely dissolved. Using the standard enthalpies of formation of the product and reactants, we can solve for the value of Hrxn for all strong acids in their first ionization with a strong base, which turns out to be -55.8kJ/mol. However, the theoretical value for the H rxn of acetic acid and a strong base is -56.1kJ/mol.Therefore, acetic acid is not a strong acid. c. Write the net ionic equation for the reaction between HA and NaOH. CH3COOH(aq) + OH(aq) H2O(l) + CH3COO(aq)

4. A calorimeter similar to your Styrofoam-ball calorimeter was used to determine the enthalpy change associated with the reaction between Cu and Zn(s). The reaction between 20mL of 0.450M CuSO4 and 0.264g Zn(s) resulted in a temperature change of 8.83C.

Prior to the analysis, the calorimeter was calibrated using the reaction between 15mL of 2.0M HCl and 5mL of 2.0M NaOH, which brought about a temperature change of 5.60C. a. Write the net ionic equation for the calibration reaction H(aq) + OH(aq) H2O(l)

b. Write the net ionic equation for the displacement reaction Zn(s) + Cu(aq) c. Calculate Ccal Zn(aq) + Cu(s)

d. Calculate the enthalpy change (per mole) for the displacement reaction.

5. Given that the standard enthalpy of formation of liquid water, H f,H2O is -285kJ/mol, calculate the Hf of OH(aq).

Appendix

Equation used to calculate the heat capacity of the calorimeter We start with three basic equations: (1) (2) (3) Where qcal = heat of the calorimeter

qcal = -qrxn qcal = CcalT qrxn = nlrHrxn T = change in temperature nlr = moles of limiting reactant Hrxn = enthalpy per mole of reaction

qrxn = heat of reaction Ccal = heat capacity of the calorimeter

Using equation 1, we can equate equation 2 and 3 by substitution. We are left with:

CcalT = -nlrHrxn
We isolate Ccal on one side, and we now have the final equation:

Ccal = (-nlrHrxn) T

Equation used to determine the heats of reaction for reactions 1-6 and reactions 7 and 8 For reactions 1-6:

qrxn = -CcalT
For reactions 7 and 8:

qrxn = -(mc + Ccal)T

Where qrxn = heat of reaction

m = mass of precipitate c = specific heat of precipitate

Ccal = heat capacity of the calorimeter T = change in temperature