# By adding Equations 1, 2, and 3, the Overall Equation is obtained. Summation of their enthalpies gives the enthalpy of formation for MgO.

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1 The standard enthalpy of formation of a compound, Hf o, is the heat change accompanying the formation of one mole of compound from the elements at standard state. The standard state of a substance is the most stable physical form of the compound at one atmosphere pressure and 25 C. Elements in their standard states are assigned a Hf o value of zero. The overall heat change is: Hrxn o = Hf o (Products) Hf o (Reactants) The Hf of a compound can be determined by synthesizing one mole of the compound and measuring the heat change by calorimetry. If the energy of the system increases at the expense of the surroundings, the reaction is endothermic. If energy flows from the system to the surroundings, the reaction is exothermic. We will work with magnesium oxide, MgO, in this experiment. The Hf o of MgO is the heat produced when one mole of Mg combines with one-half mole of O2 at standard conditions: Overall Equation Mg(s) + ½ O2(g) -----> MgO(s) When it is impossible or inconvenient to perform a single-step synthesis of one mole of a compound, chemists can still calculate the H of a reaction by using stoichiometry and Hess s Law. We can produce any quantity of desired compound, then relate the measured heat change, q, to the quantity produced and find heat change per mole. Also, Hess s Law states that when a reaction is performed in a series of steps, rather than directly, the sum of the heat changes for each step equals the overall heat change for the reaction. We will apply Hess s Law to determine the enthalpy of formation of MgO by performing a series of reactions, measuring their heat change, then summing the reactions and heats to find the Hf for MgO. Equation 1 Mg(s) + 2 H + (aq) Mg 2+ (aq) + H2(g) H1 Equation 2 Mg 2+ (aq) + H2O(l) MgO(s) + 2 H + (aq) H2 Equation 3 H2(g) + ½O2(g) H2O(l) H3 Overall Equation Mg(s) + ½ O2(g) MgO(s) Hf = H1+ H2+ H3 By adding Equations 1, 2, and 3, the Overall Equation is obtained. Summation of their enthalpies gives the enthalpy of formation for MgO. We will not perform the reaction described in Equation 3 since hydrogen gas is explosively flammable. You will use the accepted value for the enthalpy change of this reaction, kj/mol. For convenience we perform the reverse of Equation 3 by mixing solid MgO with dilute aqueous acid. This reaction is rapid and exothermic while the reverse is not spontaneous at standard conditions. The reverse of Equation 3 has identical H but opposite sign.

2 Also, we will not be working at standard conditions, so we cannot find H. Normal laboratory conditions are close to standard conditions, however, and allow a close approximation. Finally, every calorimeter absorbs some of the heat released in the reaction. The heat required to raise the temperature of the calorimeter by 1 C is the calorimeter constant, Ccal. We must determine Ccal for a particular calorimeter (a Thermos bottle), then use the same calorimeter for the rest of the experiment. PROCEDURE Wear your safety glasses while doing this experiment. Step 1 Determination of the Calorimeter Constant. Check out a calorimeter and record its code number. Measure out 50.0 ml of cold water, pour it into the calorimeter and allow it to remain for three minutes to reach thermal equilibrium with the calorimeter. Read and record the temperature of the cold water (Tc) to the nearest 0.1 C. Heat another sample of water to approximately 60 C then remove the flame. Pour 50.0 ml of hot water into a graduated cylinder, read and record its temperature (Th) then IMMEDIATELY pour the hot water into the calorimeter. Stopper the calorimeter to prevent heat loss, swirl to mix for approximately one minute then read the temperature of the mixture of hot and cold waters (Thc). Repeat the procedure for at least 3 trials. Calculation of the calorimeter constant The general formula for heat absorbed or released by a substance is: q = c m T where q is the heat, c is the specific heat of the substance in J g 1 C 1, m is the mass of the substance and T is the temperature change, T = Tfinal Tinitial. Since this experiment is performed under constant pressure conditions, q can also be expressed as H. The heat lost by the hot water equals the heat gained by the cold water plus the heat gained by the calorimeter (Law of Conservation of Energy): 0 = Hhot water + Hcold water + Hcalorimeter or 0 = (c m T)hot water + (c m T)cold water + (Ccal)( Tcal) Since the only unknown is Ccal we can calculate the heat capacity of the calorimeter. No mass is needed to find the heat absorbed by the calorimeter since its mass is constant throughout the experiment. The T for the cold water and the calorimeter are equal since they were originally in contact.

3 Step 2 Determination of H1 Carry out this step AWAY FROM ANY FLAME! Dry the calorimeter. BE CAREFUL; the lining is fragile. Measure out 60.0 ml of 1.00 M HCl and pour it into the calorimeter. Let the calorimeter stand to equilibrate while weighing the magnesium metal. Weigh a clean vial on the top-loading balance. Place g of magnesium metal into the vial and weigh, recording the total mass. Record the temperature of the HCl solution in the calorimeter then carefully but quickly pour the Mg metal into the acid solution. IMMEDIATELY cover the opening but LEAVE THE STOPPER LOOSE to allow the hydrogen gas to escape. Gently swirl the calorimeter, taking care not to spill any of the solution. Record the maximum temperature reached by the solution. DO NOT USE THE THERMOMETER AS A STIRRER; it must remain immersed in the solution. Empty and dry the calorimeter. Repeat the procedure. Calculation of H1 Assume that all the heat released by the reaction was absorbed by the HCl solution and by the calorimeter. Also assume that the density and specific heat of the dilute aqueous 1.00 M HCl solution are the same as that of pure water: density equals 1.00 g/ml and specific heat equals J g 1 C 1. We will first calculate the heat, q1, in kj for the amount of Mg used in the experiment. Then we calculate H1 for one mole of Mg. Note that q and H1 will be negative since the reaction is exothermic. Then, 0 = q1 + qhcl + qcalorimeter or: q1 = -[(c m T)HCl + (Ccal)( Tcal)] H1= q 1 g Mg 24.31g Mg x 1mol Mg Step 3 Determination of H2 Measure 60.0 ml of 1.00 M HCl solution into the dry calorimeter. Place about 0.95 g of MgO in a clean vial and record the mass. Record the temperature of the HCl solution in the calorimeter. Pour the weighed MgO into the calorimeter, taking care to empty all the sample quickly into the solution. Immediately stopper the calorimeter tightly (no gas is evolved in this reaction) and gently swirl the mixture. Record the maximum temperature reached by the mixture. Weigh the vial with any residue. Find the total mass of MgO used in the experiment by difference. Repeat the procedure.

4 Calculation of H2 Calculate q for the second experiment in the same manner as for the first experiment. Then, remember that the reaction whose enthalpy we want is THE REVERSE of the reaction performed in the laboratory. Finally, convert q2 to H2 by calculating the amount of heat for one mole of MgO, using a calculation similar to step 2. Calculation of Hf for magnesium oxide For your calculated values of H1 and H2, find the mean value and range for each. Use the experimental values for H1 and H2 and the given value for H3 to calculate the enthalpy of formation of MgO. Include an expression of the uncertainty in your answer equal to one-half of the difference of the values.

5 Section Name Pre-laboratory Assignment 1. How much heat is absorbed by a 550. g sample of water as it warms from 22.5 C to 47.1 C? 2. Calculate H for the reaction: GeO(s) + ½ O2(g) GeO2(s) by combining the enthalpies of these two known equations, using Hess ss Law. Ge(s) + ½O2(g) GeO(s) H = -255 kj GeO2(s) Ge(s) + O2(g) H = +535 kj 3. In determining H1, the thermometer registers an increase in temperature for the solution in the calorimeter. What change occurs to the chemical potential energy of the Mg(s) and the HCl(aq) in the experiment?

6 Section Report Sheet Name I. Determination of the Calorimeter Constant Calorimeter # Trial 1 Trial 2 Trial 3 Calculation of Ccal Tc (cold water) Th (hot water) Thc (mixture) Tc = Tcal Th Ccal Mean value for calorimeter constant (show units) Show one complete sample calculation of Ccal above. II. Determination of H1 Trial 1 Trial 2 Weight of Mg + vial Calculation of H1 Weight of vial Weight of Mg Mass of HCl solution Ti (initial T of HCl) Tf (final T of HCl) THCl = Tf Ti q1 (heat released by rxn) Moles of Mg used H1, kj/mol Mg Mean value of H1 Show one complete calculation for H1 above.

7 Report (continued) III. Determination of H2 Trial 1 Trial 2 Weight of MgO + vial Calculation of H2 Weight of vial + residue Mass of MgO used Mass of HCl solution Ti (initial T of HCl) Tf (final T of HCl) THCl = Tf Ti q2 (heat released by rxn) Moles of MgO used H2, kj/mol MgO (remember the sign change!) Mean value of H2 Show one complete calculation for H2 above. IV. Determination of Hf for MgO Show your calculation below, including the deviation from the mean. Hf for MgO, deviation = Calculation:

8 Section Name Post Laboratory Questions 1. When pure sulfuric acid dissolves in water, a great deal of heat is liberated. To determine the enthalpy of solution, 175 g of water was placed in an open calorimeter and cooled to 20.0 C. Then 5.00 g of pure, concentrated sulfuric acid, H2SO4(l), also at 20.0 C, was added and mixed in. The temperature rose rapidly to 25.4 C. Assume that the specific heat of the solution is J g 1 C 1. Ccal = 19 J/ C. Calculate q. Then, calculate the H of solution for one mole of H2SO4. 2. Suppose that during the determination of H2 all the MgO did not dissolve in the HCl solution before the final temperature reading was obtained. What effect would this have on your calculated Hf value? 3. The standard enthalpy of formation for MgO(s) is kj/mol. Calculate the % error for your experimental value.

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