EXPERIMENT NO.2 CALORIMETRY Fajardo, Jemimah Andrea P. Salunga, Joezelle H. AB1, Grp #2, Prof.

Michael Tan April 29, 2012

Abstract In this experiment, the heat changes within reactions were observed using an improvised calorimeter. Heats, such as specific heat and heat capacity were determined in the experiment in order to get the solutions heat of fusion and heat of neutralization. Also, the calorimeter constant specifically for a certain calorimeter was determined, which is a crucial part in the experiment, for it was used in the other parts of the experiment as well. To evaluate the said properties, a three-part methodology was used. Various computations with regards to thermochemistry were done and these experimental results were then compared to the theoretical values and errors and discrepancies were accounted for. By using the calorimeter, the heat changes within the system were effectively measured. Since, the calorimeter does not allow for any heat exchange between the system and its surroundings, the overall heat of the system was preserved. It is important to learn calorimetry because any process that involves heat change is a candidate for a calorimetric study. Because it involves heat, calorimetry is used in designing drugs in the pharmaceutical industry, in quality control of process streams in the chemical industry, and the study of metabolic rates in biological systems. Keywords: calorimetry, heat of fusion, heat of neutralization, heat capacity, specific heat

Introduction Chemical reactions involve breaking and making of molecular bonds, thus involve change in temperature. When these substances undergo changes in temperature, the heat loss or absorbed can be calculated using the equation: q = mST, where q is the heat loss or absorbed, S is the specific heat, m is the mass and T is the change in temperature. Furthermore, the product of the mass of the substance and the specific heat is equal to the heat capacity. The specific heat (S) heat is defined as the amount of heat needed to raise 1 gram of a substance by 1C, while the heat capacity (C) is the amount of heat needed to raise a given quantity of a substance to 1C. These changes in heat cannot be measured in an open system but can only be possible in a closed system calorimeter. A calorimeter allows exchange of matter but not of heat thus, preserving the systems original heat and allow accurate measurement of heat change. It is used to measure heat flow, or the heat changes in physical and chemical processes. It is a tightly closed container used to prevent heat and energy from coming out, and is hence treated as an isolated system, where the total heat is equal to 0. A real calorimeter has two chambers one for measuring the volume of water and the other for holding the reaction you want to measure. Both chambers are insulated so that the heat stays within the system. The two chambers are separated by a metal wall so as to allow the flow of heat from the

reaction to the water. A thermometer is used to measure the temperature of the system and the calorimeter is sealed around it so that no heat or water can escape. In using the calorimeter, a known amount of water is placed within the water chamber. The temperature of the water is to be recorded. Then, a known amount of substance to be studied is placed within the other chamber. The thermometer is then observed for any changes in the temperature. Using a calorimeter, different heats can be measured for this experiment the heats of fusion and neutralization. The molar heat of fusion is defined as the energy required to melt 1 mole of a solid. Aside from heat capacity and specific heat, some substances also have the heat of fusion and heat of neutralization. Heat of fusion (Hf) is the amount of heat needed to change a substances phase from solid to liquid. The heat of neutralization is the amount of heat released when one mole of water is formed from the neutralization between a hydrogen ion from an acidic solution and a hydroxide ion from a basic solution. All in all, these heats are needed to identify the changes in temperature within a system. There are two types of calorimeter: a constantvolume calorimeter and a constant-pressure calorimeter. A constant-volume bomb calorimeter measures the heat of combustion by placing a known mass of a compound in a steel container filled with oxygen at about 30 atm of pressure before being placed in a bucket with water and a thermometer attached to it. It is ignited electrically

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and the heat produced from the ignition is measured through the change in temperature. It was given the name bomb because of the explosive nature of the reaction (on a small scale) in presence of excess oxygen gas. One importance of the constant-volume calorimeter is that it measures the energy contents of food and fuel. The second type of calorimeter is simpler to create and can be formed out of two styrofoam cups where the outer cup insulates the reacting mixture from the surroundings. Then, two solutions of known volume containg reactants of the same temperature are carefully mixed in the calorimeter. It is used to determine the heat change of noncombustion reactions and the heat effects of a variety of reactions like the acid-base neutralization, heat of solution, and heat of dilution. Like the constant bomb calorimeter, the heat produced is determined by the change in temperature. Experimental The experiment was divided into three parts: evaluation of the calorimeter constant, evaluation of the heat of fusion of ice, and evaluation of the heat of the reaction for three sets. The calorimeter was first set up. Two styrofoam cups were used. About one inch was cut from the edge of one cup for the two cups to fit each other. A hole was also pierced through the cover cup for the thermometer. For part A, evaluation of the calorimeter constant, 60 mL of tap water was placed into the calorimeter equipped with a thermometer and three successive identical readings were recorded as the initial temperature of the calorimeter and the tap water. Then, 40 mL of tap water was heated to 50 to 60C. This hot water was immediately transferred into the calorimeter containing the tap water. The equilibrium temperature was taken by reading the temperature every three seconds until it remained constant for four successive readings. This equilibrium temperature is the final temperature. For the second part, evaluation of the heat of fusion, accurately 60 mL of tap water was again transferred to the same calorimeter equipped with a thermometer after the previous contents were disposed of. The temperature was recorded until three successive readings were identical. The final reading was recorded as the initial temperature of the calorimeter and tap water for part B. Meanwhile, a beaker lined with tissue paper at the bottom was weighed. About 10 to 15 grams of ice was added into the said beaker and it was weighed again. The

ice was transferred into the calorimeter containing the tap water. The temperature was read only after all the ice has melted. The temperature was read every three seconds until the reading remains constant for four successive readings. The calorimeter was constantly shaken in between readings. The equilibrium temperature was recorded as the final temperature. For the last part, evaluation of the heat of reaction, the following sets of reagents were used:
Table 1. Reagents used for each set.

Set I Set II Set III

4.5 mL 6 M HCl + 5.5 mL 6 M NaOH 4.5 mL 6 M HOAc + 5.5 mL 6 M NaOH 4.5 mL 6 M HCl + 5.5 mL NH4OH

The temperature for each reagent in each set was recorded. The reagents were mixed in one calorimeter and the temperature was read every three seconds until a constant temperature was obtained. Results The following data were gathered for the evaluation of the calorimeter constant:
Table 2A. Initial data values for the determination of the calorimeter constant.

Initial mass Initial temp.

Tap water 60 grams 34 C

Hot water 40 grams 67 C

Table 2B. Data values for change in temperature over time for the determination of the calorimeter constant.
Time (s) Temp. (C)

0 34

3 39

6 41

9 44

12 46

15 47

18 47

21 47

24 47

50 40 30 20 10 0 0 10 20 30
Figure 1. Plot of temperature (y-axis) vs. time (x-axis) for the Evaluation of the Calorimeter Constant.

The final/equilibrium temperature for the evaluation of the calorimeter constant was 47C. Through calculations, the calorimeter constant for the said calorimeter was 1.54 cal/C.

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The following information represents the data gathered for the evaluation of the heat of fusion:
Table 3A. Initial data values for the determination of the heat of fusion of ice.

The final temperature for the evaluation of the heat of reaction of Set I was 62C. Its heat of reaction was calculated to be -11,522.96 cal/mol. For the second set the initial temperature was 33C.
Table 4B. Data values for change in temperature over time for the determination of the heat of reaction for Set II. Time (s) 0 3 6 9 12 15 18 21 24 27 Temp. (C)

Initial mass Initial temp.

Tap water 60 grams 35 C

Ice 11.82 grams 0 C

The following table and graph shows the basis for the final temperature.
Table 3B. Data values for change in temperature over time for the determination of the of the heat of fusion of ice. Time (s) 0 3 6 9 12 15 18 21 Temp. (C)

33

35

38

39

41

44

47

49

53

54

35

33

30

27

21

21

21

21

40 20 0 0 5 10 15 20 25
Figure 2. Plot of temperature (y-axis) vs. time (x-axis) for the Evaluation of Heat of Fusion of Ice.

60 50 40 30 20 10 0 0 10 20 30
Figure 4. Plot of temperature (y-axis) vs. time (x-axis) for the Evaluation of Heat of Reaction of Set II.

The final/equilibrium temperature for the evaluation of the heat of fusion of ice was 21C. Through calculations, the heat of fusion of ice was computed to be 72.89 cal/g. The following tables and graphs present the bases for the final temperature of each of the three reactions: For the first set the initial temperature was 40C.
Table 4A. Data values for change in temperature over time for the determination of the heat of reaction for Set I.
Time (s) Temp. (C) 0 40 3 42 6 44 9 45 12 46 15 52 18 54 21 56 24 59 27 62

The final temperature for the evaluation of the heat of reaction of Set II was 54C. Its heat of reaction was calculated to be -9,825.93 cal/mol. The initial temperature for the third set was 38C.
Table 4C. Data values for change in temperature over time for the determination of the heat of reaction for Set III. Time (s) 0 3 6 9 12 15 18 21 24 27 Temp. (C)

38

38

39

39

40

40

42

43

44

45

46 44 42 40 38 36 0 10 20 30
Figure 5. Plot of temperature (y-axis) vs. time (x-axis) for the Evaluation of Heat of Reaction of Set III.

80 60 40 20 0 0 10 20 30
Figure 3. Plot of temperature (y-axis) vs. time (x-axis) for the Evaluation of Heat of Reaction of Set I.

The final temperature for the evaluation of the heat of reaction of Set III was 45C. Its heat of reaction was calculated to be -3,923.70 cal/mol.

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Discussion For this experiment, it must be noted that a constantpressure calorimeter was used. As was mentioned, the experiment was divided into three parts: calorimeter constant, heat of fusion, and heat of reaction. In calorimetry, it is very important to determine first the Ccal or the heat capacity of the calorimeter to determine the amount of heat absorbed or released in the process (Chang, 2010). The Ccal varies from one calorimeter to another because it depends on the efficiency of the calorimeter and the way it was made. However, upon the determination of the calorimeter constant, that certain calorimeter can now be used to measure the heat of combustion of other substances , as well as the amount of heat required to raise the temperature of the calorimeters contents by a change in temperature In the first part of the experiment, the calorimeter constant was to be detemined. Since the calorimeter is treated as an isolated system, wherein there is no exchange of matter and energy with the surroundings, we can say that the total heat of the system is 0. Therefore, qcal + qtap water + qhot water = 0 and is further supported by the first law of thermodynamics which states that energy is neither created nor destroyed. Hence, the energy released by a part of the system is equal to the energy absorbed by another part of the system. Thus, rearranging the equation above, -qhot water = qcal + qtap water (equation 1) The negative sign in -qhot water indicates an exothermic process because of the release of energy by the hot water when it was mixed with initial system which has the lower temperature and thus, absorbs the energy released by the hot water. The mass of the tap water can easily be calculated given that the density of water is 1 g/mL, and having 60 mL of water, the mass will then be 60 grams. The initial temperature of the calorimeter and tap water (34C) was readily available, as well as the constant specific heat of water, given by 4.184 J/C, which is equal to 1 cal/gC. Apparently, the 40 mL tap water that was supposed to be heated to 50 to 60 C was heated to 67C, therefore, the initial temperature of the hot water was 67C. The final temperature was 47C, which is in between the initial temperature of the calorimeter and tap water and the initial temperature of the hot water. The explanation for this is shown above. Hence, given the values, Ccal Chem 18.1, Calorimetry

can now be calculated: As was mentioned in the introduction, q = mst. !!"# + !!"#$"!%& + !!!"#$"%& = 0 !!"# !" + (mst)!"#$"!%& + (mst)!"#$%#&' = 0 (mst)!"#$"!%& (mst)!"#$%#&' !!"# = !"
60! !!"# = 1!"# !! 47 ! 34 ! 40! (47 ! 34 ! ) 1!"# (47 ! 67 ! ) !!

!!"# =

!. !"#$% !!

For the second part of the experiment, the heat of fusion of ice was to be determined experimentally. The system is composed of the calorimeter, tap water, and ice water. The heat of fusion is defined as the heat needed to melt all ice into ice water. Again, this is an isolated system, therefore, !!"# + !!"#$"!%& + !!"#$%&#' = 0 Following the principle regarding the First Law of Thermodynamics used in the first part of the experiment, it is expected that ice water, having a lower temperature compared to the other members of the system, will absorb the energy from these other parts of the system, which have a higher temperature. Hence, the equation will be !!"#$%&#' = (!!"# + !!"#$"!%& ) (equation 2) From the data gathered, the initial temperature of the calorimeter and tap water (35C), and ice water (0C). The weight of the beaker with tissue paper was 113.75 grams while the weight of beaker with tissue paper and ice was 125.57 grams, hence, subtracting the former from the latter value would yield a value of 11.82 grams, which is the weight of the ice. Upon the melting of all the ice into the calorimeter, the final temperature was recorded to be 21C. The heat of fusion can now be calculated: Manipulating equation 2,
60! 1!"# !! 21 ! 35 ! + 1.54!"# (21 ! 35 ! ) = !!"#$%&#' !!

!!"#$%&#' = !"#. !" !"# !!"# !"# 11.82 ! !"# =

!!"# !!"# !!"# !!"#

= !". !"

!"# !

The theoretical molar heat of fusion of water is 6.01 kJ/mol or 79.72 cal/g. The molecular heat of fusion calculated is very near because it was made sure

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that all the ice melted when the equilibrium temperature was reached. As for the last part of the experiment, the heat of reaction was needed to be determined for each set. The system involves the calorimeter, the acid, the base, and the reaction. The acid and the base will react with each other, forming water, because the + acid ionizes into H ions while the base ionizes into OH ions, thus, these ions will combine and form water molecules. This process releases energy, and is thus, an exothermic reaction, with the rest of the system being endothermic. Since qH20 = qacid + qbase, the equation would then be: !!"# = (!!"# + !!"#$% ) The data gathered regarding the temperature for varies for each set: Initial temp. (C) Final temp. (C) Set I 34 62 Set II 34 54 Set III 34 45 For Set I, qrxn = - qsoln qcal = (-MHCl)(SHCl)( THCL)(-MNaOH)(SNaOH) ( TNaOH)(Ccal)(TCal) =(-4.5g)(1.0cal/q*c)(29)(-5.5g)(1.0cal/q*c)(25)(.154)(28) = -311.12 cal HCl: M1V1=M2V2 6M (0.0045L)=M2(0.01L) =2.7 M 2.7M=m/0.01L m = 0.027 mols HCl NaOH: M1V1=M2V2 6M (0.0045L)=M2(0.01L) =3.3 M 3.3M=m/0.01 m = 0.033 mols NaOH mols of LR: 0.027 mols ! !!"".!" !"# !!"# = !"# = = - 11,522.96 cal/mol
!!" !.!"# !"#$

=(-4.5g)(1.0cal/q*c)(10)(-5.5g)(1.0cal/q*c)(8)(.154)(11) = -105.94 cal HCl: M1V1=M2V2 6M(0.0045L)=M2(0.01L) =2.7M 2.7M=m/0.01L m = 0.027mols HCl NaOH: M1V1=M2V2 6M (0.0055L)=M2(0.01L) =3.3M 3.3M=m/0.01 m = 0.033 mols NaOH mols of LR: 0.027 mols !!"# =
!!"# !!"

!!"#.!" cal !.!"# !"#$

= -3 923.70 cal/mol

The difference in the calorimeter constants was due to the different calorimeters used for each set. The volume for acids and bases was constant throughout, thus the molarity of the acid and the base for each set is the same with the other sets. The limiting reagents for the three sets are the bases. This is because the reactions involve a 1:1 relationship between the acid and the base, and since the volume of the bases are relatively smaller than the acids, the resulting number of moles will also be lesser thant that of the acids, making them the limiting reagents. The molar heat of neutralization of Set I (strong acid and strong base) was the largest, followed by Set II (weak acid and strong base), and finally, by Set III (strong acid and weak base). The standard heat of neutralization for a strong acid and base is -13.695 kcal/mol. Set I has its heat of neutralization closer to that of the standard because it involved hydrochloric acid (HCl), which is a strong acid, and sodium hydroxide (NaOH), which is a strong base. Set II involves a weak acid- acetic acid (HOAc), and a strong base- sodium hydroxide (NaOH) thus having a smaller heat of neutralization than that of a strong acid and strong base. Also, Set III involves a strong acid- hydrochloric acid (HCl) and a weak base- ammonium hydroxide (NH4OH) thus also having a smaller heat of neutralization. The difference in the heat of neutralization of weak acids and weak bases is because they do not dissociate completely and during dissociation, heat is absorbed resulting to a lesser total heat evolved during neutralization. The theoretical values for the heats of neutralization for sets I to III are -13.48 kcal/mole, -11.92 kcal/mole and -13.42 kcal/mole respectively. Theoretically,Set II is smallest but experimentally, it is Set III. These differences may be due to inaccuracy in taking the temperature and calorimeter constants, differences in external factors when the theoretical values were taken, and calorimeter used, especially its efficiency. Conclusions and Recommendations Page 5 of 6

For Set II, qrxn = - qsoln qcal = (-MHOAc)(SHOAc)( THOAc)(MNaOH)(SNaOH) ( TNaOH)(Ccal)(TCal) =(-4.5g)(1.0cal/q*c)(24)(-5.5g)(1.0cal/q*c)(23)(.154)(20) = -265.3 cal HOAc: M1V1=M2V2 6M(0.0045L)=M2(0.01L) =2.7 M 2.7M=m/0.01L m = 0.027 mols HCl NH4OH: M1V1=M2V2 6M(0.0055L)=M2(0.01L) =3.3 M 3.3M=m/0.01 m = 0.033 mols NaOH mols of LR: 0.027 mols ! !!"#.! !"# !!"# = !"# = = - 9 825.93 cal/mol
!!" !.!"# !"#$

For Set III, qrxn = - qsoln qcal = (-MHCl)(SHCl)( THCL)(-MNH4OH)(SNH4OH) ( TNH4OH)(Ccal)(TCal) Chem 18.1, Calorimetry

The amount of heat change during reactions is difficult to know especially if it occurred in an open system. That is why it is important to use a calorimeter when measuring the heat change. When using a calorimeter, it will be impossible for heat to escape the system and it will be possible to calculate the exact change in heat. When solving for the heat the heat capacity is multiplied by the change in temperature and where heat capacity is calculated by multiplying the mass of the substance by its specific heat. In part A of the experiment the calorimeter constant was calculated where the heat of the calorimeter is divided by the change in heat. It was found out that o the groups calorimeter constant is 1 cal/ C. In part B, the heat of fusion (Hf) of ice was calculated and the experimental Hf had a very large departure from the theoretical Hf of ice, implying that errors were made during the experiment. In part C, the heat of reaction (Hneut) or the heat released when one mole of water is formed between an acid and a base of three different set ups were calculated. The difference in their Hneut is caused by their ionization. Strong electrolytes ionize completely, thus forming more moles of water while weak electrolytes have only partial ionization, thus having lower Hneut than that of the strong electrolytes. The errors that occurred in the results could be caused by experimental or human errors. It is highly recommended that a real calorimeter is used in the experiment to prevent any heat to escape and to have more accurate results, otherwise, immediately close the lid upon adding the substances in the

container and ensure that the lid of the container is tightly closed before measuring the temperature and. Also, for part B, it is recommended to make sure that all the ice has been melted before taking the equilibrium temperature to account for a more accurate measurement for the heat of fusion of ice. References Barett, J. How Does a Calorimeter Work? Retrieved Apr 18, 2012, from http:// www.ehow.com/howdoes_4925148_a-calorimeter-work.html. Brown, et al. (2009). Chemistry: The Central Science. Philippines. Pearson Education South Asia PTE. LTD. Chang, R. (2010). Chemistry (10 NY: McGraw-Hill.
th

ed.). New York,

Enthalpy of Neutralization. Retrieved Apr 18, 2012, from http://faculty.ccri.edu/aahughes/GenChemII/ Lab%20Experiments/Enthalpy_of_Neutralization.pdf We hereby certify that we have given substantial contribution to this report.

JEMIMAH ANDREA P. FAJARDO

JOEZELLE H. SALUNGA

Chem 18.1, Calorimetry

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