Calorimetry is the science of measuring the heat of chemical reactions or physical changes. Calorimetry is performed with a calorimeter.

The word calorimetry is derived from the Latin word calor, meaning heat. Scottish physician and scientist Joseph Black, who was the first to recognize the distinction between heat and temperature, is said to be the founder of calorimetry. Indirect calorimetry calculates heat that living organisms produce from their production of carbon dioxide and nitrogen waste (frequently ammonia in aquatic organisms, or urea in terrestrial ones), OR from their consumption of oxygen. Lavoisier noted in 1780 that heat production can be predicted from oxygen consumption this way, using multiple regression. The Dynamic Energy Budget theory explains why this procedure is correct. Of course, heat generated by living organisms may also be measured by direct calorimetry, in which the entire organism is placed inside the calorimeter for the measurement. Observations: The temperature was calibrated for each of these observations using a previously-made calibration curve. It is attached with interpolation lines drawn in. A. Heat Capacity of Calorimeter Temperature of calorimeter and water before mixing (observed): 21.5 .2 C Temperature of calorimeter and water before mixing (adjusted): 18.5 .2 C Temperature of warm water (observed): 46.0 .2 C Temperature of warm water (adjusted): 43.0 .2 C B. Heat of Neutralization of HClNaOH Temperature of calorimeter and NaOH (observed): 23.0 .2 C Temperature of calorimeter and NaOH (adjusted): 20.0 .2 C C. Heat of Neutralization of HC2H3O2NaOH Temperature of calorimeter and NaOH (observed): 22.0 .2 C Temperature of calorimeter and NaOH (adjusted): 19.0 .2 C Graphs of temperature versus time for each of the three parts of the experiment can be found at the end of this report, clearly labeled. These graphs were used for the results in the next section. All of these graphs represent adjusted temperatures as interpolated on the calibration curve.

A widely used modern instrument is the differential scanning calorimeter, a device which allows thermal data to be obtained on small amounts of material. It involves heating the sample at a controlled rate and recording the heat flow either into or from the specimen. Discussion: The values obtained are experimental data that must be compared to the true value in order to gauge the accuracy of the experiment. The true value of the joules released per mole of water for the HCl reaction is 58.2 kJ/mol. The true value of the joules released per mole for the acetic acid reaction is 55.8 kJ/mol.

Percent error, HCl reaction. (65 kJ 58.2 kJ) / 58.2 kJ *100 = 11.68% error. Percent error, acetic acid reaction. (75 kJ 55.8 kJ) / 55.8 kJ *100 = 34.41% error. These are astronomical percent errors. There were major mistakes with equipment and procedure. A few sources of error that could account for the discrepancies are the measuring devices themselves. A graduated cylinder was used to measure volume. A buret or pipet should have been used for maximum accuracy. Using a graduated cylinder leaves room for a crucial error in volume determination, which would then lead to errors in determination of mass, molar content of the solution, and every other derivative formula. Not only could an inaccurate amount of solution be poured into the cylinder, but not all of this solution may be poured out. There are always extra drops of solution clinging to the walls of a cylinder. This would have negatively influenced volume readings. In addition, the thermometer had to be calibrated, which improves accuracy but is itself an imprecise technique. A better thermometer could have prevented errors in temperature readings. Also, it is assumed that the specific heat of the solution is the same as the specific heat of water, and that the tap water used in the experiment contains negligible impurities. Neither of these assumptions should be made, as slight discrepancies can cause larger discrepancies in calculations later in the experiment. The theory associated with this experiment deals with potential energy in molecules. Heat was released by molecules in this reaction. This heat came from potential energy stored in chemical bonds. When the bonds were broken and new bonds were formed, energy was released. This experiment serves to verify the atomic theory and the observations made about chemical bonds. In addition, various parts of this experiment relied on the atomic theory, such as the determination of the number of moles of solute in a solution. The ramifications for this experiment are broad. First, experience in the laboratory was gained. Secondly, the energy of a system was studied. Anything can be classified as a system and its energy can be studied. This experiment related the way that energy behaves in a system. Energy is released by commonplace reactions; if this energy could be harnessed, it could be used. This is the driving force behind hydrogen fuel cells. Hydrogen and oxygen are mixed, producing water, but also producing massive amounts of energy. The formation of water was the driving force of this metathesis reaction, and it produced energy. Also, we must find the change in temperature of a solution to determine the heat absorbed by solution. In order to find the change in temperature, a graph of temperature versus time must be constructed (as outlined in the Procedure). This graph will look like the graph presented in Figure 26.2:

Figure 26.2 serves to show the graph and explain its components. In this experiment, after finding the heat capacity of the calorimeter, we'll neutralize two acids and calculate the heat of neutralization. Those two acids are hydrochloric acid and acetic acid. You should use 1.0 M solutions of each, or you might burn your eyeballs out.

Heat of Solution of Sulfuric Acid

Concepts
The objective of this experiment is to determine the heat of solution of sulfuric acid. H2SO4 (l) H+ (aq) + HSO4- (aq) The procedure for this experiment is similar to that for determining the heat of solution of ammonium nitrate. A small glass bulb containing pure sulfuric acid is placed in a calorimeter containing water. When the bulb is broken, the sulfuric acid dissolves in the water, and the heat from the reaction is released to the water and the calorimeter. This experiment adds a degree of realism to the experimental procedure. To this point, it has been assumed that the calorimeter is perfectly insulated and no heat enters or leaves the system from the surroundings. In practice, the insulation is not perfect and there is some heat loss or gain.

If the system is at room temperature initially, the initial temperature of the system will be stable. The final temperature, however, will not be at room temperature. If the reaction is exothermic, the final temperature will be above room temperature, and heat will slowly be lost from the calorimeter to the surroundings. Instead of being constant, the final temperature will slowly drift downward. The converse is true for an endothermic reaction. To compensate for this heat loss/gain, the temperature is measured as a function of time. Prior to the initiation of the chemical reaction, the temperature vs time plot can be used to establish the initial baseline. When the reaction is complete, the temperature vs time plot can be used to establish the final baseline. These baselines are typically linear, especially if the calorimeter is well-insulated, which makes the heat loss/gain relatively small. The baselines represent the temperature changes attributable to heat exchange from the surroundings. To determine Ti and Tf, imagine that the reaction took place instantaneously and the heat from the reaction is instantly distributed evenly throughout the system. In this hypothetical case, the temperature would instantaneously jump from Ti to Tf at the time the reaction was initiated. These temperatures cannot be measured directly, but they can be inferred by extrapolating the baselines to obtain the temperatures on the initial and final baselines at the time the reaction was initiated. (Strictly speaking, initial and final temperature reading should be taken at the "effective" initial time, which is not exactly the time when the reaction was initiated. For the purposes of this virtual experiment, the time when the experiment was initiated will be used.)

Experiment
Objective:

Determine the heat of solution of sulfuric acid.

Approach:

Dissolve sulfuric acid in water in a calorimeter. Monitor the variation of the temperature with time. Determine baselines for the times before the reaction started and after the reaction finished. Extrapolate the baselines to the reaction time to obtain the initial and final temperatures. Calculate the heat of solution of sulfuric acid.

Enter values for the masses of water and sulfuric acid (FW 98.08) and start the experiment. The temperature is sampled at 0.5 sec intervals and automatically plotted on the graph. The temperature vs time data is listed in a separate window. The heat capacity of the calorimeter is 288. J oC-1 The reaction is initiated at t = 5.00 sec, which is marked on the graph by a vertical black line.

Numerical values of the experimental data are shown in the columns at the right. Under the "Initial Baseline" column, select the points you wish to use to establish the baseline prior to initiation of the reaction. By holding down the control or shift key, it is possible to select multiple points on this list. After you have selected the points, click the "Plot Initial Baseline" button in the main browser window. The initial baseline will be displayed on the graph, and the slope and intercept will be listed. In general, the initial baseline is well-defined and linear, and you should use all of the points prior to the initiation of the reaction to construct the initial baseline. Carefully examine the points near the end of the experiment at long times after the reaction is finished and the system is slowly cooling. Select a number of points from the linear region of the data to determine the final baseline. The purpose of the baselines is to determine the initial and final temperature that would have been observed had the reaction occurred instanteously and had the heat from the reaction been distributed uniformly throughout the system instantaneously. (This is obviously a hypothetical situation.) Use the mouse to read the temperatures at t = 5.00 sec (the reaction starting time) that lie on the initial (Ti) and final (Ti) baselines. When the cursor is over the graph, press the left mouse button to obtain a crosshair cursor and to display the time and temperature at the position of the cursor. Carefully position the mouse on the desired point. Alternatively, one can use the slope and intercept for each baseline to calculate the temperature at 5.00 sec.

Objective: - Enthalpy of Dissociation Introduction: In all chemical and physical changes that occur in nature, heat energy is either absorbed or evolved. The heat flow that occurs at constant pressure is quantitatively referred to as the enthalpy of reaction (Hrxn). Depending on the type of reaction studied, Several types of enthalpies of reactions can be determined, Like the enthalpy of neutralization, heat of formation and heat of solution. The enthalpy change for any reaction can be determined experimentally using the following relationship:
Hsys = Hrcn = - Hsurr

The enthalpy change for the reaction that is occurring is equal in magnitude but opposite in sign to the heat change in the contents of the calorimeter. This is because the measured temperature is that of the solution in the calorimeter which is responding to enthalpy change in the reaction under investigation. This means that you will not measure the enthalpy change of reaction directly but merely its effect on the surrounding environment.

In this experiment, you will measure the heat capacity of a simple cub calorimeter. Then using Hess law, you will calculate the enthalpy of dissociation of the following reaction: CH3COOH+ H2O CH3COO-(aq)+ H3O+(aq) (1) Calculations involved: The surrounding, namely the solution and the calorimeter, absorbs the energy evolved by any chemical reaction. The heat ( q ), absorbed by the calorimeter, is calculated from the following equation: q = m C T Where: C is the heat capacity pf the calorimeter measured in J/oC.
T is the temperature change in the reaction solution.

The heat absorbed by solution is given by the following equation: q = m Cp T Where: m is the mass of the solution.
T is the temperature change in the reaction solution

Cp is the specific heat of the solution, measured in J/g oC. Since enthalpy change is an extensive property, the amount of heat generated by the reaction is given by the expression. q = n. H Where: n is the number of moles of a specific reaction.
H is the enthalpy change measured in KJ/mol.

In the first part of this experiment, you will measure the heat capacity of a simple calorimeter. Then the heats of neutralizations of acid base reactions ( HCl - NaOH; CH3COOH NaOH ) will be measured and used to calculate the heat of dissociation of acetic acid ( reaction 1 )

Materials and equipment: Tow beakers ( 100, 150 ml ). ; HCL solution (2.0M ). Thermometer. ; NaOH solution ( 2.0M ). Graduated cylinders ( 50, 100 mL ).; Acetic acid ( 2.0M ). A.1: Heat of neutralization of HCL NaOH reaction: H+(aq)+OH-(aq) H2O(1) ; Hneul In this part of experiment, you must use the calibrated calorimeter. 1. Place about 25 ml of 2.0M HCL solution in the calorimeter calibrated in the previous step and then measure its temperature. 2. Introduce 25 ml of 2.0M NaOH solution in the other beaker. 3. With the thermometer placed in HCL solution, pour the 25 ml of NaOH solution into the acid solution stirring gently with the thermometer. Record the highest temperature observed. 4. After the solution cools to room temperature, weigh the calorimeter and its contents. 5. Tabulate your data follows Trial ( 1 ) Mass of dry empty 100 ml beaker 2.47 g Mass of 100 ml beaker + NaCL solution 52.37 Mass of NaCL solution 52,37-2,47=49,9 Initial temperature of HCL solution 21 Highest temperature after mixing 25 Change in temperature observed t 37 Heat gained by the calorimeter = t = t3-((t1+ t2)/2) = 37 ( 21 + 15 )/2) = 14oC

Heat gained by the solution = H = q/n Heat lost by the reaction = q = m. t. sp q = 49,9 * 13 * 4,184 q = 2922, 9 Moles of water formed = * n = m.v = ( 25/1000 ) * 2 = 0,05 mol.
Hrxn ( KJ/mol H2O ) = H = q/n H = ( 2922.9/0.05 )/1000 = 58,458

A.2: Heat of neutralization of acetic acid: CH3COOH + NaOH CH3COO-Na+(aq)+ H2 ;Hneul 1. Repeat exactly the steps mentioned in part.2 replacing the HCl solution with acetic acid solution. 2. Tabulate your data as follows. Trial Mass of dry empty 100 ml beaker 2.47 Mass of 100 ml beaker + acetate solution 52.88 Mass of sodium acetate solution 50.41 Initial temperature of acetic acid solution( ti ) 22 Maximum temperature after mixing ( t max ) 25 Change in temperature observed t (22+25)/2=23.5 Heat gained by the calorimeter = 33

Heat gained by the solution = 9.5

Heat lost by the reaction = H1 = q/n q = m*t*sp= 50.41* 9.5 * 4.189 = 2003.6 n = m.v= 2 * 0.025 = 0.05
H1= q/n H1= ( 2003.6 / 0.05 ) 1000 = 40.027

Moles of water formed = H2 = q/n q = m * t * sp 50.41 * 9.5 * 3.95 = 1891.6 n = 0.05

H2 = ( 1891.6 / 0.05 ) 1000 = 37.8 Hrxn ( KJ/mol H2O ) = H(diss) = H1+ H2 = 40.027 + 37.8 = 77.827

A.3: Heat of dissociation of weak acid: The Heat of dissociation of acetic acid is calculated by the application of Hess's law on the following equations: H2O H+(aq) + OH- (aq) ; H1 CH3COOH(aq) + OH- (aq) CH3COO-Na+(aq) + H2O(I) + ) ; H2 CH3COOH(aq) CH3COO (aq) + H (aq) ; Hdiss Hdiss = H1 + H2 Heat of dissection of acetic acid = Some useful data: Specific heat of water = 4.184 J/g.oC Specific heat of 1.0M sodium acetate solution ( CH3COONa ) = 3.95 J/g.oC Post- laboratory Questions 1. In this experiment, KOH solution and HCl solutions were used to measure enthalpy of neutralization. Will this value change if HNO3 is used instead of HCl solution?

2. Will the results concerning enthalpy of neutralization change if 1.0M solution of Mg ( OH )2 is used instead of 2.0M NaOH solution.? Why? No, because Mg ( OH )2 can give us 2 mole of OH. Discussion: * We should be very careful when we use HCl because HCl is a strong acid. * We should take the temperature of maximum very careful because it's gone up fast then start go down.
Calculate the theoretical (true) enthalpy of neutralization in kJ per 1.00 mole water from heats of formation data given on page 12. H = nHf products nf reactants. Calculate the % error between the two results. % Error = (Exptl Value True Value) x 100% divided by True Value % Error can be + or depending whether the experimental value is greater or less than the true value.

Conclusion: The experiment was successful to the degree that the procedure was carried out
correctly. Equipment problems and other unavoidable sources of error served to cause a large percent error for each part of the experiment. However, the techniques associated with calorimetry were practiced, providing valuable experience.

http://onlinelibrary.wiley.com/doi/10.1002/cjce.21689/full http://www.ausetute.com.au/heatcapa.html http://pessoa.fct.unl.pt/p110316/Articles/calorimeter.pdf