HESSS LAW

A. Identity Objectives : 1. To learn the magnitude of the reaction heat of reaction that takes place with different processes. 2. To prove the Hesss law Date : Monday, 12th March 2012 (0913031032) (0913031045) (0913031055) (0913031057)

Nama Kelompok : 1. Ni Putu Mei Purnawidiastini 2. Luh Ami Yuliantika 3. Luh Ayu Sriningsih 4. Ni Putu Yani Novi Arysanti B. Theory

Most compounds cannot be synthesized directly from its elements. In some cases, the reaction is too slow or side reactions occur that produce substances other than the expected compound. In these cases Hf0 can be determined by an indirect approach, based on the Law of heat summation (or Hess's Law). Hess's Law can be stated "When the reactants are converted into products, enthalpy changes is same, regardless of whether the reaction takes place in one stage or in several stages" (Chang, 2003). In other words, if we can divide the reaction into several stages of reaction where H0reaction can be measured, we can calculate H0reaction for the overall reaction. Hess's Law is based on the fact that since H is a state function, H depends only on the initial state and final state (only on the nature of the reactants and products). Enthalpy change will be the same whether the overall reaction takes place in one stage or multiple stages. Useful analogy for Hess's Law is as, suppose you go from ground floor to the sixth floor of a building with escalators. The increase in gravitational potential energy is obtained (which corresponds to a change of overall enthalpy process) will be the same, regardless of whether you go straight up or stop at every floor on the way up (divided into several stages of reaction). Based on the exposure Hess's Law above it can be made a chart that shows two lines of stages with the same end result. Direction 1 E A+B F Direction 2 1 C+D

But it may also not only the direction is direction 1 and direction 2, but there is also the third, the fourth and so on. In this experiment will be seen whether the energy in the direction 1 is similar reaction to the energy in the direction 2. If solid sodium hydroxide is reacted with hydrochloric acid 4M the reaction is as follows. Direction 1

NaOH(s) aq NaOH(aq,4M) NaOH(aq,4M) HCl (aq,4M) NaCl (aq,2M) H 2 O (l)

Direction 2

H1 H 2

HCl (aq,4M) aq HCl (aq,2M)

H 3

HCl (aq,2M) NaOH(s) NaCl (aq,2M) H 2 O (l) H 4

Where: s = solid l = liquid aq = water added until the certain concentration Both of the reactions also can show as bellow Direction 1 NaOH(aq,4M) + HCl(aq,4M) H direction 1 = H1 +H2 H direction 2 = H3 + H4 NaOH(aq,2M) + H2O(l)

NaOH(s) + HCl(aq,4M)

NaOH(s) + HCl(aq,2M) Direction 2 An exothermic reaction releases heat, and that heat flows into the surroundings and is usually observed as a temperature increase in the solvent, container and other immediate surroundings. An insulated container called a bomb calorimeter can be used to limit the heat flow with good accuracy to the solvent and bomb. Thus -qreaction = qsolution + qbomb Equation 1 The "q" is the symbol for heat flow which will be measured in Joules. The negative sign on the left of the equation says that heat is flowing out of the reaction; so the heat flow out of the reaction is equal to the heat flow into the solution and the calorimeter. It is very important to remember that whenever heat is flowing out of a substance or reaction the value of "q" will be negative. In the case of our experiment, the calorimeter absorbs so little heat that qbomb is nearly zero and thus the equation simplifies to 2

-qreaction = qsolution Equation 2 The temperature change caused by the addition of a given amount of heat will depend on the specific heat, Csp, of the substance. The specific heat of water (and a good approximation for dilute aqueous solutions) is 4.18 J/g oC. Thus, the heat involved can be calculated by the equation q = (Csp)(m)(T) .Equation 3 The mass of the substance is m, and the change in temperature is T. Change in temperature is always calculated as (final temperature) - (initial temperature). The enthalpies of these directly observed reactions and Hess's Law will be used to calculate the enthalpy change for an additional reaction which is not directly observed. Recall that since enthalpy is a state function, the enthalpy change for any process will depend only on the starting and ending points, not on the reaction path followed. The enthalpy, (H(A-B), change for the reaction AB can be calculated by adding up the enthalpy changes for a series of intermediate steps. ACDB Thus, H(A-B) = H(A-C) + (C-D) + (D-B). This concept is especially useful in calculating the enthalpy change for reactions which are not easy to observe or measure directly.

C. MATERIALS AND EQUIPMENTS Materials and equipments table Equipments Calorimeter Stirring rod Graduated cylinder glass 25 mL Beaker glass 100 mL Beaker glass 250 mL Dropping pipette Heater Thermometer 100 C Spatula Watch glass
0

Amount 1 piece 1 piece 1 piece 2 pieces 1 piece 1 pieces 1 piece 2 pieces 1 piece 2 pieces

Materials Aquades Solid NaOH HCl (4M) solution

Amount 50 mL 8.1580 grams 50 mL

D. PROCEDURES AND OBSERVATION RESULTS No. Direction 1 1 The materials and equipments that will Materials and equipments already prepared be used was prepared firstly 2 As much as 4.0760 grams of solid NaOH in white solid that have Procedures Observation Results

NaOH was weighed in the closed bottle hygroscopic properties with mass 4.0760 because the NaOH have hygroscopic grams properties

25 mL of aquades was measured by The volume of aquades thats used is 25 using graduated cylinder glass, and mL entered into calorimeter while shaked. After that the temperature was noted start from the first minutes until the third minutes.

At the of four minutes, was added After the solid NaOH was added into the 4.0760 grams of solid NaOH into the calorimeter and shaken, so the NaOH calorimeter little by little while stirring dissolve properly and on the wall of until homogeneous and the temperature calorimeter is warm. was noted of five minutes until of twenty eight minutes.

As much as 25 mL of HCl 4 M, was The volume of chloride acid 4M that use is noted the temperature at the eleventh 25 mL minutes, then it was added into 4

calorimeter. ( Directly pour after the NaOH dissolved). That mixture was stirred in the calorimeter and note the temperature begin at twenty eight minutes until gotten the constant

temperature. Direction 2 1 25 mL of aquades was measured by The volume of aquades thats used is 25 using graduated cylinder glass, and mL entered into calorimeter. After that the temperature was noted start from the first minutes until the third minutes.

25 mL of HCl 4M solution was The volume of chloride acid 4M that use is measured, noted and entered into 25 mL

calorimeter at fourth minutes. The temperature of solution was noted start from fourth minutes until seven minutes. 3 4.0820 grams of solid NaOH was NaOH in form of white solid that have entered into calorimeter little by little hygroscopic properties and shaken directly in seven minutes. The temperature was noted in fourth teen minutes until the temperature almost constant.

Observation results data First Direction Time (minutes) 0 0.5 1 1.5 Temperature(oC) 29 29.5 29.5 29.5 Time (minutes) 14 14.5 15 15.5 Temperature(oC) 38.2 38.2 38 37 5

2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 7 7.5 8 8.5 9 9.5 10 10.5 11 11.5 12 12.5 13 13.5

Adding of solid NaOH 31 31 31.5 33 39 44 46 45.8 45.8 45.1 45.1 44.1 43.3 42.9 41.2 41 40.5 40 40 39.8 39.7 39 38.8

16 16.5 17 17.5 18 18.5 19 19.5 20 20.5 21 21.5 22 22.5 23 23.5 24 24.5 25 25.5 26 26.5 27

37 37 Adding of HCl 4 M 48.5 48 47.2 47 46.8 46 45.5 45 44.8 44.2 44 43.5 43.1 43 43 42.9 42.9 42 42 42

Second Direction Time (minutes) 0 0.5 1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 6 6.5 Temperature(oC) 28 27.5 27.5 27.5 Adding of HCl 4 M solution 30 32 32 32 Adding of solid NaOH 33 38 42 47 Time (minutes) 11.5 12 12.5 13 13.5 14 14.5 15 15.5 16 16.5 17 17.5 18 Temperature(oC) 54 53.5 53 52.5 52 51.5 51 50.5 50 49.5 49 48.5 48 48 6

7 7.5 8 8.5 9 9.5 10 10.5 11

55 58 57.5 57 56.5 56 55.5 55 54.5

18.5 19 19.5 20 20.5 21 21.5 22

47.5 47.5 47 46.5 46 46 46 46

E. DISCUSSION In this experiment conducted proof of Hess's Law using a calorimeter. According to Hess's Law magnitude of the enthalpy of a reaction is not determined by the way or step of the reaction, but only determined by the initial state and final state of a reaction. The basic of Hess law is the enthalpy or internal energy, where the magnitude is a magnitude that does not depend on the way of the reaction. The magnitude of the enthalpy can be determined only by knowing the heat of reaction alone. Enthalpy change is an extensive nature, namely the change is directly proportional to the number of substances involved in the reaction, in addition to the enthalpy change of reaction will change when the direction of turn. Sometimes a reaction takes place via one path or two paths, but the results are the same. In the determination of neutralization heat of strong acid and strong base, was conducted by reacting HCl (acid) and NaOH (base) through two direction readtion that producing NaCl salt. Reaction between HCl and NaOH also can be said as salting reaction because produce salt, where the enthalpy change that is occurred was measured by using calorimeter. In this experiments was conducted an experiment about Hess Law by using calorimeter. This experiment was conducted by two directions. First direction was used 4 gram of sodium hydroxide solid. Amount 25 mL of aquades was poured into the calorimeter. Then, the temperature of water was take noted while stirred. The temperature change of water was observed until constant. From the observation result was obtained the constant temperature of water is 29,5oC. After the temperature of water is constant, then solid sodium hydroxide was added little by little. The solution was stirred, and observe the temperature change until the temperature is constant. The addition of NaOH causing the temperature increase, constant 7

temperature after the addition of sodium hydroxide is 37oC. In this case, energy that was released calculated as H1 with temperature change T1. After the temperature of solution was constant, then added by hydrochloric acid 4 M directly. The addition of HCl causing the temperature increase fastly. This means was occurred releasing the amount of energy. Measuring the temperature was done Take noted the temperature change until the temperature is constant. The constant temperature after added by HCl is 42oC. Energy that was released calculated as H2 with temperature change is T2. Then the first direction finished and continued by the second direction. From the experiment data above, can be created curve relationship between temperature toward time from experiment First direction.

Curve of relationship between Temperature towards Time in First Direction Experiment

51 46 Temperature 41 Addition of water 36 31 26 0 5 10 15 Time (minutes) 20 25 30 Addition of NaOH Addition of HCl

The calculation process as follows. Known : m1 NaOH = 4,076 g Mr NaOH = 40 water Cwater Vwater m water = 1 g/mL = 4,18 J/goC = 25 mL = water x V water 8 Ccalorimeter = 58,67 J/oC

= 1 g/mL x 25 mL = 25 g T1 Mr HCl V HCl HCl [HCl] T2 = (37 29,5)oC = 7,5oC = 36,5 = 25 mL = 1,19 g/mL = 4M = (48,5 37)oC = 11,5oC

H1 : H2O(l) + NaOH(s) NaOH(aq) q reaction = -(q solution + q calorimeter) H1 =

q reaction mol

q solution

= m c T1 = (m1 + m) c T1 = (4,076 g+ 25g) x 4,18 J/goC x 7,5 oC = 911,53 Joule

q calorimeter = C T1 = C T1 = 58,67 J/oC x 7,5 oC = 440,025 Joule So, the heat reaction is : q reaction = -(q solution + q calorimeter) q reaction = -(911,53 + 440,025) Joule q reaction = - 1351,55 Joule Negative sign (-) means that energy is released to the surrounding amount 1351,55 Joule H1 =
- 1351,55 J q reaction = - 13263,54 J/mol == 4,076/40 mol mol

H2 : NaOH(aq) + HCl(aq) NaCl(aq ) + H2O(l) mol =MxV = 4 M x 25 mL = 100 mmol massa = 100 mmol x 36,5 mg/mmol = 3650 mg = 3,65 g m2 HCl = 3,65 g q solution = m c T2 9

= (m1 + m2) c T2 = (4,076 g+ 3,65g) x 4,18 J/goC x 11,5oC = 371,38 Joule q calorimeter = C T2 = C T2 = 58,67 J/oC x 11,5oC = 674,705 Joule So, the heat reacton is : q reaction = -(q solution + q calorimeter) q reaction = -(371,38 + 674,705) Joule q reaction = - 1046,085 Joule Negative sign (-) means the energy is released to the surrounding amount 1046,085 Joule. H2 =
q reaction - 1046,085 J = = - 10460,85 J/mol 0,1 mol mol

So, H for First direction

= H1 + H2 = (-13263,54 - 10460,85) J/mol = - 23724,39 J/mol = - 23,724 kJ/mol

The next steps for the second direction reaction is the opposite of the first direction reaction. The first step was conducted in second direction reaction is used 25 mL of aquades that is inserted in the calorimeter and its temperature is recorded. The constant temperature of water is 27.5oC. Furthermore the addition of HCl solution temperature is 30oC in aquades calorimeter has been completed. This measures the temperature of the HCl solution to 32oC and its constant. In this case, the energy released is calculated as H1 with the change in temperature T1. When the solid NaOH is added, an increase in temperature is 33oC. Temperatures continue to rise until the NaOH reacts exhausted and constant temperature is 46C, from the change in temperature is seen that the release of heat by the system are absorbed by the calorimeter. At this stage can be determined H2 by the temperature change T2. From the experiment data above, can be created curve relationship between temperature toward time from experiment second direction.

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Curve of relationship between Temperature towards Time in Second Direction Experiment

56 51 Temperature 46 Addition of water 41 36 31 26 0 5 10 15 Time (minutes) 20 25 30 Addition of HCl Addition of NaOH

The calculation process as follows. Known : m1 NaOH = 4,082 g Mr NaOH = 40 water = 1 g/mL = 4,18 J/goC = 25 mL = water x V water = 1 g/mL x 25 mL = 25 g Mr HCl V HCl [HCl] HCl T3 T4 = 36,5 = 25 mL =4M = 1,19 g/mL = (32 27,5)oC = 4,5oC = (46 32)oC = 14oC Ccalorimeter = 58,67 J/oC Cwater V water m water

Dissolution reaction HCl : 11

H3 : HCl(aq) + H2O(l) H3O+ + Clmol =MV = 4 M x 25 mL = 100 mmol mass = 100 mmol x 36,5 mg/mmol = 3650 mg = 3,65 g m2 HCl = 3,65 g q solution = m c T3 = (m2 + m) c T3 = (4,082 g+ 25g) x 4,18 J/goC x 4,5oC = 547,032 Joule q calorimeter = C T3 = C T3 = 58,67 J/oC x 4,5oC = 264,015 Joule So, reaction heat is : q reaction = -(q solution + q calorimeter) q reaction = -(547,032 + 264,015) Joule q reaction = - 811,047 Joule Negative sign (-) means that eneregy is released to the surrounding amount 811,047 Joule. H3 =
q reaksi - 811,047J = 0,1 mol mol

= - 8110,47 J/mol

Reaksi : H4 : HCl(aq) + NaOH(aq) NaCl(aq ) + H2O(l) q solution = m c T4 = (m1 + m2) c T4 = (4,082 g+ 3,65 g) x 4,18 J/goC x 14oC = 452,48 Joule q calorimeter = C T4 = C T4 = 58,67 J/oC x 14 oC = 821,38 Joule So, the reaction heat is : q reaction = -(q solution + q calorimeter) 12

q reaction = -(452,48 + 821,38) Joule q reaction = - 1273,86 Joule Negative sign (-) means that energy is released to the surrounding amount 1273,86 Joule. H4 =
q reaction = - 1273,86 J = - 12482,70 J/mol mol (4,082/40) mol

So, H for second direction = H3 + H4 = (-8110,47 12482,70) J/mol = - 20593,17 J/mol = - 20,60 kJ/mol The magnitude of the enthalpy change in first direction and the second direction is little difference in the amount that is 3,124 kJ/mol. The enthalpy change for the first direction is 23,724 kJ/mol and for the second direction is 20,60 kJ/mol. Hess's Law states that, the enthalpy of the first direction equal to the enthalpy of the second direction. Its mean that the data of experiment is appropriate with the Hess Law, because the differences only 3,124 kJ/mol. In this experiment only occurs little bit deviation, which is maybe caused by existence of procedural errors committed by observer where NaOH is added by observer is not at the same range time either direction 1 or direction 2. Moreover, it can also be possible to use materials that have been contaminated by impurities substances, given the materials used (NaOH) is hygroscopic, so that the materials used in these experiments no longer purely the result of observations obtained was not optimal, precision tools less, and less rigorous in observing temperature changes that occur.

F. CONCLUSION Based on the experiments and the observation results can be concluded that: 1. Hess's Law states that the magnitude of the enthalpy of a reaction is not determined by the way or step of the reaction, but only determined by the initial state and final state of a reaction. 2. The enthalpy reaction of first direction is 23,724 kJ/mol and the enthalpy reaction of second direction is 20,60 kJ/mol. The difference between enthalpy of first direction and second direction is relatively small only 3,124. Its mean that the result of experiment is appropriate or suitable according to the Hess Law, which is said that the enthalpy of the first direction equal to the enthalpy of the second direction because the difference relative small.

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G. QUESTION ANSWER 1. What is the Hesss Law statement? Answer: Hess's Law can be stated as follows "When the reactants are converted into products, enthalpy changes together, regardless of whether the reaction takes place in one stage or in several stages" (Chang, 2003). There is also another formulation of the Hesss Law according Suardana , et al stated that Hess's Law states that "The amount of heat released or absorbed in chemical reactions do not depend on the course of the reaction, but only depends on the initial and final state of reaction." 2. Write down the Hesss Law in this experiment! Answer: For the experiment 1 (first direction) can be formulated the Hesss Law is as follows: HCl(aq) + NaOH(aq) NaCl(aq ) + H2O(l) HCl(aq) + H2O(l) H3O+ + ClFor the experiment 2 (second direction) can be formulated the Hesss Law is as follows: NaOH(aq) + HCl(aq) NaCl(aq ) + H2O(l) H2O(l) + NaOH(s) NaOH(aq)

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REFERENCES

Bird, Tony. 1987. Penuntun Praktikum Kimia Fisik untuk Universitas. Experiments in Physical Chemistry. Jakarta: Gramedia Chang, Raymond. 2003. Kimia Dasa Konsep-Konsep Inti Jilid 1. Jakarta : Erlangga Suardana, I Nyoman, I Made Kirna dan I Nyoman Retug. 2001. Buku Ajar Kimia Fisika I. Singaraja : Ikip Negeri Singaraja

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